Organometallic chemistry of diphosphazanes. Part 26. Ruthenium hydride complexes of chiral and achiral diphosphazane ligands and asymmetric transfer hydrogenation reactions

The half-sandwhich ruthenium chloro complexes bearing chelated diphosphazane ligands, [(eta(5)-Cp)RuCl{kappa(2)-P,P-(RO)(2)PN(Me)P(OR)(2)}] [R = C6H3Me2-2,6] (1) and [(eta(5)-Cp*)RuCl{kappa(2)-P, P-X2PN(R)PYY'}] [R = Me, X = Y = Y' = OC6H5 (2); R = CHMe2, X-2 = C20H12O2, Y = Y' = OC6H5 (3) or OC6H4'Bu-4 (4)] have been prepared by the reaction of CpRu(PPh3)(2)Cl with (RO)(2)PN(Me)P(OR)(2) [R = C6H3Me2-2,6 (L-1)] or by the reaction of [Cp*RuCl2](n) with X2PN(R)PYY' in the presence of zinc dust. Among the four diastereomers (two enantiomeric pairs) possible for the "chiral at metal" complexes 3 and 4, only two diastereomers (one enantiomeric pair) are formed in these reactions. The complexes 1, 2, 4 and [(eta(5)-Cp)RuCl {kappa(2)-P,P-Ph2PN((S)-*CHMePh)PPhY)] [Y = Ph (5) or N2C3HMe2-3,5 (SCSPRRu)-(6)] react with NaOMe to give the corresponding hydride complexes [(eta(5) -Cp)RuH {kappa(2)-P,P-(RO)(2)PN(Me)P(OR)(2)}] (7), [(eta(5)-Cp*)RuH {kappa(2)-P,P'-X2PN(R)PY2)] [R = Me, X = Y = OC6H5 (8); R = CHMe2, X-2 = C20H12O2, Y = OC6H4'Bu-4 (9)] and [(eta(5) -Cp)RuH(kappa(2)-P, P-Ph2PN((S)-*CHMePh)PPhY)][Y =Ph (10) or N2C3HMe2-3,5 (SCSPRRu)(11a) and (SCSPSRu)-(11b)]. Only one enantiomeric pair of the hydride 9 is obtained from the chloro precursor 4 that bears sterically bulky substituents at the phosphorus centers. On the other hand, the optically pure trichiral complex 6 that bears sterically less bulky substituents at the phosphorus gives a mixture of two diastereomers (11a and 11b). Protonation of complex 7 using different acids (HX) gives a mixture of [(eta(5)- Cp)Ru(eta(2)-H-2){kappa(2)-P, P-(RO)(2)PN(Me)P(OR)(2))]X (12a) and [(eta(5)-Cp)Ru(H)(2){kappa(2)-P, P-(RO)(2)PN(Me)P(OR)(2)}]X (12b) of which 12a is the major product independent of the acid used; the dihydrogen nature of 12a is established by T, measurements and also by synthesizing the deuteride analogue 7-D followed by protonation to obtain the D-H isotopomer. Preliminary investigations on asymmetric transfer hydrogenation of 2-acetonaphthone in the presence of a series of chiral diphosphazane ligands show that diphosphazanes in which the phosphorus centers are strong pi-acceptor in character and bear sterically bulky substituents impart moderate levels of enantioselectivity. Attempts to identify the hydride intermediate involved in the asymmetric transfer hydrogenation by a model reaction suggests that a complex of the type, [Ru(H)(Cl){kappa(2)-P,P-X2PN(R)PY2)(solvent)(2)] could be the active species in this transformation. (c) 2007 Elsevier B.V. All rights reserved.

Rationalizing the effects of amino acid side chain, pyridine, and imidazole on the assembly and reversible disassembly of a octanuclear Cu(III) complex

This paper reports the observation of a reversible disassembly process for a previously reported octanuclear Cu(II) complex with imidazole. To identify the factors responsible for the process, five Cu(II) complexes of different nuclearity with different amino acid-derived tetradentate ligands were structurally characterized. The results show that the coordination geometry preference of Cu(II), the tendency of imidazole to act as in-plane ligand, and H-bonding played important role in the formation and disassembly of the octanuclear complex. A general scheme describing the effect of different amino acid side arms, solvents, and exogenous ligands on the nuclearity of the Cu(II) complexes has been presented. The crystals of the complexes also showed formation of multifaceted networks in the resulting complexes.

Excitation energy transfer from a fluorophore to single-walled carbon nanotubes

We study the process of electronic excitation energy transfer from a fluorophore to the electronic energy levels of a single-walled carbon nanotube. The matrix element for the energy transfer involves the Coulombic interaction between the transition densities on the donor and the acceptor. In the Foumlrster approach, this is approximated as the interaction between the corresponding transition dipoles. For energy transfer from a dye to a nanotube, one can use the dipole approximation for the dye, but not for the nanotube. We have therefore calculated the rate using an approach that avoids the dipole approximation for the nanotube. We find that for the metallic nanotubes, the rate has an exponential dependence if the energy that is to be transferred, h is less than a threshold and a d(-5) dependence otherwise. The threshold is the minimum energy required for a transition other than the k(i,perpendicular to)=0 and l=0 transition. Our numerical evaluation of the rate of energy transfer from the dye pyrene to a (5,5) carbon nanotube, which is metallic leads to a distance of similar to 165 A degrees up to which energy transfer is appreciable. For the case of transfer to semiconducting carbon nanotubes, apart from the process of transfer to the electronic energy levels within the one electron picture, we also consider the possibility of energy transfer to the lowest possible excitonic state. Transfer to semiconducting carbon nanotubes is possible only if>=epsilon(g)-epsilon(b). The long range behavior of the rate of transfer has been found to have a d(-5) dependence if h >=epsilon(g). But, when the emission energy of the fluorophore is in the range epsilon(g)>h >=epsilon(g)-epsilon(b), the rate has an exponential dependence on the distance. For the case of transfer from pyrene to the semiconducting (6,4) carbon nanotube, energy transfer is found to be appreciable up to a distance of similar to 175 A degrees.

Mixed saturated-unsaturated alkyl-chain assemblies: Solid solutions of zinc stearate and zinc oleate

The linear saturated stearic acid and the bent mono-unsaturated oleic acid do not mix and form solid solutions. However, the zinc salts of these acids can. From X-ray diffraction and DSC measurements we show that the layered zinc stearate and zinc oleate salts form a homogeneous solid solution at all composition ratios. The solid solutions exhibit a single melting endotherm, with the melting temperature varying linearly with composition but with the enthalpy change showing a minimum. By monitoring features in the infrared spectra that are characteristic of the global conformation of the hydrocarbon chain, and hence can distinguish between stearate and oleate chains, it is shown that solid solution formation is realized by the introduction of gauche defects in a fraction of the stearate chains that are then no longer linear. This fraction increases with oleate concentration. It has also been possible from the spectroscopic measurements to establish a quantitative relation between molecular conformational order and the thermodynamic enthalpy of melting of the solid solutions.

Modified density matrix renormalization group algorithm for the zigzag spin-1/2 chain with frustrated antiferromagnetic exchange: Comparison with field theory at large J(2)/J(1)

A modified density matrix renormalization group (DMRG) algorithm is applied to the zigzag spin-1/2 chain with frustrated antiferromagnetic exchange J(1) and J(2) between first and second neighbors. The modified algorithm yields accurate results up to J(2)/J(1) approximate to 4 for the magnetic gap Delta to the lowest triplet state, the amplitude B of the bond order wave phase, the wavelength lambda of the spiral phase, and the spin correlation length xi. The J(2)/J(1) dependences of Delta, B, lambda, and xi provide multiple comparisons to field theories of the zigzag chain. The twist angle of the spiral phase and the spin structure factor yield additional comparisons between DMRG and field theory. Attention is given to the numerical accuracy required to obtain exponentially small gaps or exponentially long correlations near a quantum phase transition.

Trade wars in the TRIPS Council: Intellectual property, technology transfer, and climate change

This Chapter considers the geopolitical conflicts in respect of intellectual property, trade, and climate change in the TRIPS Agreement 1994 under the World Trade Organization (WTO). In particular, it focuses upon debates in the TRIPS Council on the topic of patent law and clean energy in 2013 and 2014. The chapter highlights the development agenda of a number of developing countries who are keen for access to clean energy to combat climate change and global warming. It also considers the mixed contributions of members of the BRICS/ BASIC group – including Brazil, India, China, and South Africa. This chapter highlights the intellectual property maximalist position of a number of developed countries on intellectual property, climate change, and trade. Seeking to overcome this conflict and stalemate, this Chapter puts forward both procedural and substantial reform options in respect of intellectual property, trade, and climate change in the TRIPS Council and the WTO. It also flags that the TRIPS Agreement 1994 could well be displaced by the rise of mega-regional trade agreements – such as the Trans-Pacific Partnership (TPP), and the Trans-Atlantic Trade and Investment Partnership (TTIP).

Fluorescent resonant excitation energy transfer in linear polyenes

We have studied the dynamics of excitation transfer between two conjugated polyene molecules whose intermolecular separation is comparable to the molecular dimensions. We have employed a correlated electron model that includes both the charge-charge, charge-bond, and bond-bond intermolecular electron repulsion integrals. We have shown that the excitation transfer rate varies as inverse square of donor-acceptor separation R-2 rather than as R-6, suggested by the Foumlrster type of dipolar approximation. Our time-evolution study alsom shows that the orientational dependence on excitation transfer at a fixed short donor-acceptor separation cannot be explained by Foumlrster type of dipolar approximation beyond a certain orientational angle of rotation of an acceptor polyene with respect to the donor polyene. The actual excitation transfer rate beyond a certain orientational angle is faster than the Foumlrster type of dipolar approximation rate. We have also studied the excitation transfer process in a pair of push-pull polyenes for different push-pull strengths. We have seen that, depending on the push-pull strength, excitation transfer could occur to other dipole coupled states. Our study also allows for the excitation energy transfer to optically dark states which are excluded by Foumlrster theory since the one-photon transition intensity to these states (from the ground state) is zero.

Effect of Chain Length of Alcohol on the Lipase-Catalyzed Esterification of Propionic Acid in Supercritical Carbon Dioxide

The esterification of propionic acid was investigated using three different alcohols, namely, isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol. The variation of conversion with time for the synthesis of isoamyl propionate was investigated in the presence of five enzymes. Novozym 435 showed the highest activity, and this was used as the enzyme for investigating the various parameters that influence the esterification reaction. The Ping-Pong Bi-Bi model with inhibition by both acid and alcohol was used to model the experimental data and determine the kinetics of the esterification reaction.

Influence of tilt angle of plate on friction and transfer layer—A study of aluminium pin sliding against steel plate

In the present investigation, unidirectional grinding marks were attained on the steel plates. Then aluminium (Al) pins were slid at 0.2°, 0.6°, 1.0°, 1.4°, 1.8°, 2.2° and 2.6° tilt angles of the plate with the grinding marks perpendicular and parallel to the sliding direction under both dry and lubricated conditions using a pin-on-plate inclined sliding tester to understand the influence of tilt angle and grinding marks direction of the plate on coefficient of friction and transfer layer formation. It was observed that the transfer layer formation and the coefficient of friction depend primarily on the grinding marks direction of the harder mating surface. Stick-slip phenomenon was observed only under lubricated conditions. For the case of pins slid perpendicular to the unidirectional grinding marks stick-slip phenomenon was observed for tilt angles exceeding 0.6°, the amplitude of which increases with increasing tilt angles. However, for the case of the pins slid parallel to the unidirectional grinding marks the stick-slip phenomena was observed for angles exceeding 2.2°, the amplitude of which also increases with increasing tilt angle. The presence of stick-slip phenomena under lubricated conditions could be attributed to the molecular deformation of the lubricant component confined between asperities.

An agent based adaptive bandwidth allocation scheme for multimedia applications

Bandwidth allocation for multimedia applications in case of network congestion and failure poses technical challenges due to bursty and delay sensitive nature of the applications. The growth of multimedia services on Internet and the development of agent technology have made us to investigate new techniques for resolving the bandwidth issues in multimedia communications. Agent technology is emerging as a flexible promising solution for network resource management and QoS (Quality of Service) control in a distributed environment. In this paper, we propose an adaptive bandwidth allocation scheme for multimedia applications by deploying the static and mobile agents. It is a run-time allocation scheme that functions at the network nodes. This technique adaptively finds an alternate patchup route for every congested/failed link and reallocates the bandwidth for the affected multimedia applications. The designed method has been tested (analytical and simulation)with various network sizes and conditions. The results are presented to assess the performance and effectiveness of the approach. This work also demonstrates some of the benefits of the agent based schemes in providing flexibility, adaptability, software reusability, and maintainability. (C) 2004 Elsevier Inc. All rights reserved.

Food waste, power, and corporate social responsibility in the Australian food supply chain

By examining corporate social responsibility (CSR) and power within the context of the food supply chain, this paper illustrates how food retailers claim to address food waste while simultaneously setting standards that result in the large-scale rejection of edible food on cosmetic grounds. Specifically, this paper considers the powerful role of food retailers and how they may be considered to be legitimately engaging in socially responsible behaviors to lower food waste, yet implement practices that ultimately contribute to higher levels of food waste elsewhere in the supply chain. Through interviews with key actors in the Australian fresh fruit and vegetable supply chain, we highlight the existence of a legitimacy gap in corporate social responsibility whereby undesirable behaviors are pushed elsewhere in the supply chain. It is argued that the structural power held by Australia’s retail duopoly means that supermarkets are able to claim virtuous and responsible behaviors, despite counter claims from within the fresh food industry that the food supermarkets’ private quality standards mean that fresh food is wasted. We argue that the supermarkets claim CSR kudos for reducing food waste at the expense of other supply chain actors who bear both the economic cost and the moral burden of waste, and that this is a consequence of supermarkets’ remarkable market power in Australia.

Chain structures in alkali metal borophosphates: synthesis and characterization of K3[BP3O9(OH)3] and Rb3[B2P3O11(OH)2]

Two new alkali metal borophosphates, K-3[BP(3)o(9)(OH)(3)] and Rb-3[B2P3O11(OH)(2)], were synthesized by applying solvothermal techniques using ethanol as solvent. The crystal structures were solved by means of single-crystal X-ray diffraction (K-3[BP3O9(OH)(3)], monoclinic, C2/c (No. 15), a = 2454.6(8) pm, b = 736.3(2) pm, c = 1406.2(4) pm, beta = 118.35(2)degrees, Z = 8; Rb-3[B2P3O11(OH)(2)], monoclinic, P2(1)/c (No. 14), a = 781.6(2) pm, b:= 667.3(2) pm, c = 2424.8(5) pm, beta = 92.88(1)degrees, Z = 4). Both crystal structures comprise borophosphate chain anions. While for the rubidium compound a loop-branched chain motif is found as common for most of the chain anions in alkali metal borophosphates, the crystal structure of the potassium phase comprises the first open-branched chain with the highest phosphate content found so far in this group of compounds. Both chain anions are Closely related to known anhydrous or hydrated phases, and the structural relations are discussed in terms of how the presence of OH groups and hydrogen bonds as well as number, charge, and size of charge balancing cations influence the 3D structural arrangement. The anionic entities are classified in terms of general principles of structural systematics for borophosphates.

Heat transfer in plane Couette flow of a rarefied gas using Bhatnagar-Gross-Krook model

Using the linearized BGK model and the method of moments of half-range distribution functions the temperature jumps at two plates are determined, and it is found that the results are in fair agreement with those of Gross and Ziering, and Ziering.

Free convection heat transfer from vertical cylinders and wires

Free convection heat transfer from vertical long cylinders and wires were investigated experimentally. The experiments were designed to check the analytical results and the radius of curvature criteria formulated by the same authors. The results for water, the fluid medium used in the present set of experiments, are in excellent agreement with the theory. The results of Hama, Recesso and Christiaens, Kyte, Madden and Piret, in air are also shown to be in close agreement with proposed correlations.