Copper(II) complexes of methylated glycine derivatives: Effect of methyl substituent on their DNA binding and nucleolytic property

A set of copper(II) complexes of glycine and methylated glycine derivatives, Cu(aa)₂, consisting of C-dimethylglycine, l-alanine, N-dimethylglycine and sarcosine, was investigated for their DNA binding and nucleolytic properties by means of EPR and visible spectroscopy, and electrophoresis. They bind weakly to DNA with apparent binding constants in the range 1.8–2.9 × 10³ M⁻¹ with very similar orientation. No DNA cleavage is observed in the absence of exogenous agents. Copper(II) complexes of N-methylated derivatives bind to DNA more stereo-specifically and less strongly, and their oxidative DNA cleavage is less efficient than those of the corresponding C-methylated derivatives in the presence of hydrogen peroxide (H₂O₂) alone, or sodium ascorbate (NaHA) alone or tandem H₂O₂–NaHA. The oxidative DNA cleavage mechanism in the three systems involves a common copper(I) species. Neocuproine can inhibit DNA cleavage by these complexes.     

Asymmetric Synthesis of Enaminophosphines via Palladacycle-Catalyzed Addition of Ph(2)PH to α,β-Unsaturated Imines

A highly reactive, chemo- and enantioselective addition of diphenylphosphine to α,β-unsaturated imines catalyzed by a palladacycle has been developed, thus providing the access to a series of chiral tertiary enaminophosphines in high yields. A putative catalytic cycle has also been proposed.     

Two-photon luminescence from polar bis-terpyridyl-stilbene derivatives of Ir(III) and Ru(II)

Four structurally related iridium(III) and ruthenium(II) complexes bearing two polar terpyridyl-stilbene derived chromophores 4-(4-{2-[4-(methoxy)phenyl]ethenyl}phenyl)-2,2'-6',2'-terpyridine (ttpyeneanisole) and 4-(4-{2-[phenyl]ethenyl}phenyl)-2,2'-6',2'-terpyridine (tpystilbene) have been synthesised and characterised in the solid state and in solution. In the solid state, the dihedral angle subtending the pyridyl and tolyl groups of 27.1° in the Ir(III) complex [Ir(ttpyeneanisole)(2)]·3PF(6) is more acute than in the Ru(II) derivative [Ru(tpystilbene)(2)]·2PF(6) (35.5°), indicating the presence of a greater degree of π-delocalisation across the terpyridine unit in the former compound. Their luminescence properties in fluid solution have been investigated following both resonant and non-resonant excitation. We have shown that each of the complexes undergoes two-photon excitation when excited in the near infrared (740 to 820 nm), with two-photon absorption cross sections in the range 11-67 × 10(-50) cm(4) s photon(-1). The larger cross sections for the Ir(III) complexes reflect the differences observed in the solid state. This work therefore demonstrates that such complexes are promising as luminescent markers for 3D imaging and illustrates that simple functionalisation of the chromophores and the choice of metal can lead to marked enhancements in the two-photon cross sections (σ(2)) compared to those of simpler heteroleptic polypyridyl based derivatives.     

A container yard storage strategy for improving land utilization and operation efficiency in a transshipment hub port

This paper studies the storage yard management problem in a busy transshipment hub, where intense loading and unloading activities have to be considered at the same time. The need to handle huge volumes of container traffic and the scarcity of land in the container port area pose serious challenges for the port operator to provide efficient services. A consignment strategy with a static yard template has been used to reduce the level of reshuffles in the yard, but it sacrifices on land utilization because of exclusive storage space reservation. Two space-sharing approaches are proposed to improve on the land utilization through dynamic reservation of storage space for different vessels during different shifts. Meanwhile, workload assignment among reserved spaces will also satisfy the high-low workload balancing protocol to reduce traffic congestion in the yard. A framework which integrates space reservation and workload assignment is proposed. Experimental results show that the framework is able to provide solutions for containers handling within much less storage space, while guarantee the least yard crane deployment.     

Concurrent recordings of bladder afferents from multiple nerves using a microfabricated PDMS microchannel electrode array

In this paper we present a compliant neural interface designed to record bladder afferent activity. We developed the implant's microfabrication process using multiple layers of silicone rubber and thin metal so that a gold microelectrode array is embedded within four parallel polydimethylsiloxane (PDMS) microchannels (5 mm long, 100 μm wide, 100 μm deep). Electrode impedance at 1 kHz was optimized using a reactive ion etching (RIE) step, which increased the porosity of the electrode surface. The electrodes did not deteriorate after a 3 month immersion in phosphate buffered saline (PBS) at 37 °C. Due to the unique microscopic topography of the metal film on PDMS, the electrodes are extremely compliant and can withstand handling during implantation (twisting and bending) without electrical failure. The device was transplanted acutely to anaesthetized rats, and strands of the dorsal branch of roots L6 and S1 were surgically teased and inserted in three microchannels under saline immersion to allow for simultaneous in vivo recordings in an acute setting. We utilized a tripole electrode configuration to maintain background noise low and improve the signal to noise ratio. The device could distinguish two types of afferent nerve activity related to increasing bladder filling and contraction. To our knowledge, this is the first report of multichannel recordings of bladder afferent activity.     

Surface state on first-order ferroelectrics

In the presence of a surface the Landau-Devonshire equations of ferroelectricity must be extended to include a boundary condition. For a ferroelectric with a second-order transition in the case when the polarization p(z) increases at the surface, it is well known that a surface state occurs in a range of temperature above the bulk critical temperature t_CB . Here we explore the corresponding effect for a first-order ferroelectric. We show that a surface state can occur, but only if the surface effect is sufficiently strong. Analytic expressions are derived and illustrated for p(z), the surface value p_S =p(0) and the free energy. The transition from the paraelectric state (p=0) to the surface state is first order, and for completeness we establish the dependence of the three critical temperatures (supercooling, thermodynamic and superheating) on a boundary-condition parameter y. In a final section, we derive and illustrate expressions for p(z)in the temperature range t<t_CB .     

Turbulence structure in the immediate vicinity of the shear-free air–water interface induced by a deeply submerged jet

 A PIV based technique is developed to perform flow measurements in the vicinity of the air–water interface of a submerged confined jet. Both the interface movement and the velocity field immediately beneath it are measured simultaneously. A detailed turbulence structure in the surface influence region is thus obtained. Flow parameters evaluated without and w.r.t. the interface are quantified and compared against previous works obtained using the conventional Eulerian-based instrumentation which do not account for the interface fluctuation, and checked against analytical model characterising the turbulence close to a assumed flat air–water interface. Received: 15 March 1998/Accepted: 19 October 1998     

Pd‐Catalyzed Enantiodivergent and Regiospecific phospha‐Michael Addition of Diphenylphosphine to 4‐oxo‐Enamides: Efficient Access to Chiral Phosphinocarboxamides and Their Analogues

The palladacycle‐catalyzed asymmetric P?H addition of 4‐oxo‐enamides has been developed, which provides efficient access to phosphinocarboxamides and their analogues. Solvent‐mediated reversal of stereoselectivity (ee from +96 % to ?92 %) was observed, and the underlying mechanism that allows facile access to both enantiomers of the product by judicious choice of solvents is revealed.     

A general method for constructing curved traversable wormholes in (2+1)-dimensional spacetime

We develop a general method for constructing curved traversable wormholes in (2+1)-dimensional spacetime, by generating surfaces of revolution around smooth curves. Application of this method to a straight line gives the usual spherically symmetric wormholes. The physics behind (2+1)-d curved traversable wormholes is discussed based on solutions to the Einstein field equations when the tidal force is zero. The Einstein field equations are found to reduce to one equation whereby the mass-energy density varies linearly with the Ricci scalar, which signifies that our (2+1)-d curved traversable wormholes are supported by dust of ordinary and exotic matter without radial tension nor lateral pressure. With this, two examples of (2+1)-d curved traversable wormholes: the helical wormhole and the catenary wormhole, are constructed and we show that there exist geodesics through them supported by non-exotic matter. This general method is applicable to our (3+1)-d spacetime.     

Standpoint cosmology

An unorthodox cosmology is based on a notion of standpoint, distinguishing past from future, realized through Hilbert-space representation of the complex conformai group for 3+1spacetime and associated coherent states. Physical (approximate) symmetry attaches to eight-parameter complex Poincaré displacements, interpretable as growth of standpoint age (one parameter), boost of matter energy-momentum in standpoint rest frame (three parameters) and displacement of matter location in a compact U(1)O(4)/O(3) spacetime attached to standpoint (four parameters). An initial condition (at big bang) is characterized by a huge dimensionless parameter that breaks dilation invariance. Four major length scales are recognized, called Planck, particle, lab, and Hubble, with separations controlled by ; all physical concepts, including spacetime, depend on wideness of scale separation.