One-pot two-step mechanochemical synthesis: ligand and complex preparation without isolating intermediates

Although the use of ball milling to induce reactions between solids (mechanochemical synthesis) can provide lower-waste routes to chemical products by avoiding solvent during the reaction, there are further potential advantages in using one-pot multistep syntheses to avoid the use of bulk solvents for the purification of intermediates. We report here two-step syntheses involving formation of salen-type ligands from diamines and hydroxyaldehydes followed directly by reactions with metal salts to provide the corresponding metal complexes. Five salen-type ligands 2,2'-[1,2-ethanediylbis[(E)-nitrilomethylidyne]] bisphenol, ` salenH2', 1; 2,2'-[(+/-)-1,2-cyclohexanediylbis-[(E)-nitrilomethylidyne]] bis-phenol, 2; 2,2'-[1,2-phenylenebis( nitrilomethylidyne)]-bis-phenol, ` salphenH2' 3; 2-[[(2-aminophenyl) imino] methyl]-phenol, 4; 2,2'-[(+/-)-1,2-cyclohexanediylbis[(E)-nitrilomethylidyne]]-bis[4,6-bis(1,1-dimethylethyl)]-phenol, ` Jacobsen ligand', 5) were found to form readily in a shaker-type ball mill at 0.5 to 3 g scale from their corresponding diamine and aldehyde precursors. Although in some cases both starting materials were liquids, ball milling was still necessary to drive those reactions to completion because precipitation of the product and or intermediates rapidly gave in thick pastes which could not be stirred conventionally. The only ligand which required the addition of solvent was the Jacobsen ligand 5 which required 1.75 mol equivalents of methanol to go to completion. Ligands 1-5 were thus obtained directly in 30-60 minutes in their hydrated forms, due to the presence of water by-product, as free-flowing yellow powders which could be dried by heating to give analytically pure products. The one-armed salphen ligand 4 could also be obtained selectively by changing the reaction stoichiometry to 1 : 1. SalenH(2) 1 was explored for the onepot two-step synthesis of metal complexes. In particular, after in situ formation of the ligand by ball milling, metal salts (ZnO, Ni(OAc)2 center dot 4H(2)O or Cu(OAc)(2)center dot H2O) were added directly to the jar and milling continued for a further 30 minutes. Small amounts of methanol (0.4-1.1 mol equivalents) were needed for these reactions to run to completion. The corresponding metal complexes [M(salen)] (M = Zn, 6; Ni, 7; or Cu, 8) were thus obtained quantitatively after 30 minutes in hydrated form, and could be heated briefly to give analytically pure dehydrated products. The all-at-once ` tandem' synthesis of [Zn(salen)] 6 was also explored by milling ZnO, ethylene diamine and salicylaldehyde together in the appropriate mole ratio for 60 minutes. This approach also gave the target complex selectively with no solvent needing to be added. Overall, these syntheses were found to be highly efficient in terms of time and the in avoidance of bulk solvent both during the reaction and for the isolation of intermediates. The work demonstrates the applicability of mechanochemical synthesis to one-pot multi-step strategies.

An understanding of chemoselective hydrogenation on crotonaldehyde over Pt(111) in the free energy landscape: The microkinetics study based on first-principles calculations

Microkinetic model is developed in the free energy landscape based on density functional theory (DFT) to quantitatively investigate the reaction mechanism of chemoselective partial hydrogenation of crotonaldehyde to crotyl alcohol over Pt(1 1 1) at the temperature of 353 K. Three different methods (mobile, immobile and collision theory models) were carried out to obtain free energy barrier of adsorption/desorption processes. The results from mobile and collision theory models are similar. The calculated TOFs from both models are close to the experiment value. However, for the immobile model, in which the free energy barrier of desorption approaches the energy barrier, the calculated TOF is 2 orders of magnitude lower than the other models. The difficulty of adsorption/ desorption may be overestimated in the immobile model. In addition, detailed analyses show that for the surface hydrogenation elementary steps, the entropy and internal energy effects are small under the reaction condition, while the zero-point-energy (ZPE) correction is significant, especially for the multi-step hydrogenation reaction. The total energy with the ZPE correction approaches to the full free energy calculation for the surface reaction under the reaction condition. (c) 2011 Elsevier B.V. All rights reserved.

In situ FTIRS investigations of surface processes of Rh electrode - Novel observation of geminal adsorbates of carbon monoxide on Rh electrode in acid solution

With the help of in situ multi-step FTIR Spectroscopy, two types of adsorbed geminal CO have been observed for the first time at an electrochemically modified Rh electrode. A doublet band of two broad peaks at 2166 and 2112cm is assigned to geminal CO on Rh surface oxide (or hydroxide) produced by the electrochemical modification process, and a doublet band of two peaks near 2103 and 2033cm is ascribed to geminal CO on surface clusters of Rh formed by reduction of Rh surface oxide. Based on the evolution of FTIR spectra with the electrode potential, the surface processes of a Rh electrode, subjected to a potential cycling treatment at 1.5Vs between -0.275 and 2.4V for 2min, have been elucidated. The present results at the solid/liquid electrochemical interface were compared with those obtained at the solid/gas interface, and consistent conclusions were achieved.

Observation of the inhomogeneous spatial distribution of MeV ions accelerated by the hydrodynamic ambipolar expansion of clusters

An inhomogeneous spatial distribution of laser accelerated carbon/oxygen ions produced via the hydrodynamic ambipolar expansion of CO₂ clusters has been measured by using CR-39 detectors. An inhomogeneous etch pits spatial distribution has appeared on the etched CR-39 detector installed on the laser propagation direction, while homogeneous ones are appeared on those installed at 45°and 90°from the laser propagation direction. From the range of ions in CR-39 obtained by using the multi-step etching technique, the averaged energies of carbon/oxygen ions for all directions are determined as 0.78 ± 0.09 MeV/n. The number of ions in the laser propagation direction is about 1.5 times larger than those in other directions. The inhomogeneous etch pits spatial distribution in the laser propagation direction could originate from an ion beam collimation and modulation by the effect of electromagnetic structures created in the laser plasma.

Sensitive and specific detection of viable Mycobacterium avium subsp. paratuberculosis in raw milk by the Peptide-mediated magnetic separation (PMS)-phage assay

This study describes further validation of a previously described Peptide-mediated magnetic separation (PMS)-Phage assay, and its application to test raw cows’ milk for presence of viable Mycobacterium avium subsp. paratuberculosis (MAP). The inclusivity and exclusivity of the PMS-phage assay were initially assessed, before the 50% limit of detection (LOD50) was determined and compared with those of PMS-qPCR (targeting both IS900 and f57) and PMS-culture. These methods were then applied in parallel to test 146 individual milk samples and 22 bulk tank milk samples from Johne’s affected herds. Viable MAP were detected by the PMS-phage assay in 31 (21.2%) of 146 individual milk samples (mean plaque count of 228.1 PFU/50 ml, range 6-948 PFU/50 ml), and 13 (59.1%) of 22 bulk tank milks (mean plaque count of 136.83 PFU/50 ml, range 18-695 PFU/50 ml). In contrast, only 7 (9.1%) of 77 individual milks and 10 (45.4%) of 22 bulk tank milks tested PMS-qPCR positive, and 17 (11.6%) of 146 individual milks and 11 (50%) of 22 bulk tank milks tested PMS-culture positive. The mean 50% limits of detection (LOD50) of the PMS-phage, PMS-IS900 qPCR and PMS-f57 qPCR assays, determined by testing MAP-spiked milk, were 0.93, 135.63 and 297.35 MAP CFU/50 ml milk, respectively. Collectively, these results demonstrate that, in our laboratory, the PMS-phage assay is a sensitive and specific method to quickly detect the presence of viable MAP cells in milk. However, due to its complicated, multi-step nature, the method would not be a suitable MAP screening method for the dairy industry.

New multi-stage DC-DC converters for grid-connected photovoltaic systems

Renewable energy is high on international and national agendas. Currently, grid-connected photovoltaic (PV) systems are a popular technology to convert solar energy into electricity. Existing PV panels have a relatively low and varying output voltage so that the converter installed between the PVs and the grid should be equipped with high step-up and versatile control capabilities. In addition, the output current of PV systems is rich in harmonics which affect the power quality of the grid. In this paper, a new multi-stage hysteresis control of a step-up DC-DC converter is proposed for integrating PVs into a single-phase power grid. The proposed circuitry and control method is experimentally validated by testing on a 600W prototype converter. The developed technology has significant economic implications and could be applied to many distributed generation (DG) systems, especially for the developing countries which have a large number of small PVs connected to their single-phase distribution network. 

Adaptive backstepping droop controller design for multi-terminal high-voltage direct current systems

Wind power is one of the most developed renewable energy resources worldwide. To integrate offshore wind farms to onshore grids, the high-voltage direct current (HVDC) transmission cables interfaced with voltage source converters (VSCs) are considered to be a better solution than conventional approaches. Proper DC voltage indicates successive power transfer. To connect more than one onshore grid, the DC voltage droop control is one of the most popular methods to share the control burden between different terminals. However, the challenges are that small droop gains will cause voltage deviations, while higher droop gain settings will cause large oscillations. This study aims to enhance the performance of the traditional droop controller by considering the DC cable dynamics. Based on the backstepping control concept, DC cables are modelled with a series of capacitors and inductors. The final droop control law is deduced step-by-step from the original remote side. At each step the control error from the previous step is considered. Simulation results show that both the voltage deviations and oscillations can be effectively reduced using the proposed method. Further, power sharing between different terminals can be effectively simplified such that it correlates linearly with the droop gains, thus enabling simple yet accurate system operation and control.

High Strength Thermoplastic Bonding for Multi-channel, Multi-layer Lab-on-Chip Devices for Ocean and Environmental applications

A solvent-vapour thermoplastic bonding process is reported which provides high strength bonding of PMMA over a large area for multi-channel and multi-layer microfluidic devices with shallow high resolution channel features. The bond process utilises a low temperature vacuum thermal fusion step with prior exposure of the substrate to chloroform (CHCl3) vapour to reduce bond temperature to below the PMMA glass transition temperature. Peak tensile and shear bond strengths greater than 3 MPa were achieved for a typical channel depth reduction of 25 µm. The device-equivalent bond performance was evaluated for multiple layers and high resolution channel features using double-side and single-side exposure of the bonding pieces. A single-sided exposure process was achieved which is suited to multi-layer bonding with channel alignment at the expense of greater depth loss and a reduction in peak bond strength. However, leak and burst tests demonstrate bond integrity up to at least 10 bar channel pressure over the full substrate area of 100 mm x 100 mm. The inclusion of metal tracks within the bond resulted in no loss of performance. The vertical wall integrity between channels was found to be compromised by solvent permeation for wall thicknesses of 100 µm which has implications for high resolution serpentine structures. Bond strength is reduced considerably for multi-layer patterned substrates where features on each layer are not aligned, despite the presence of an intermediate blank substrate. Overall a high performance bond process has been developed that has the potential to meet the stringent specifications for lab-on-chip deployment in harsh environmental conditions for applications such as deep ocean profiling.

Automating fault tolerance in high-performance computational biological jobs using multi-agent approaches

Background: Large-scale biological jobs on high-performance computing systems require manual intervention if one or more computing cores on which they execute fail. This places not only a cost on the maintenance of the job, but also a cost on the time taken for reinstating the job and the risk of losing data and execution accomplished by the job before it failed. Approaches which can proactively detect computing core failures and take action to relocate the computing core's job onto reliable cores can make a significant step towards automating fault tolerance. Method: This paper describes an experimental investigation into the use of multi-agent approaches for fault tolerance. Two approaches are studied, the first at the job level and the second at the core level. The approaches are investigated for single core failure scenarios that can occur in the execution of parallel reduction algorithms on computer clusters. A third approach is proposed that incorporates multi-agent technology both at the job and core level. Experiments are pursued in the context of genome searching, a popular computational biology application. Result: The key conclusion is that the approaches proposed are feasible for automating fault tolerance in high-performance computing systems with minimal human intervention. In a typical experiment in which the fault tolerance is studied, centralised and decentralised checkpointing approaches on an average add 90% to the actual time for executing the job. On the other hand, in the same experiment the multi-agent approaches add only 10% to the overall execution time