Synthesis and characterization of novel oxotechnetium (99Tc and 99mTc) and oxorhenium complexes from the 2,2'-bipyridine (NN)/thiol (S) mixed-ligand system

The synthesis and characterization of oxotechnetium and oxorhenium mixed-ligand complexes of the general formula MO[NN][S](3) (M = (99)Tc and Re), where NN represents the bidentate ligand 2,2'-bipyridine and S represents a monodentate thiophenol, is reported. The complexes were prepared by ligand exchange reactions using (99)Tc-gluconate and ReOCl(3)(PPh(3))(2) as precursors for the oxotechnetium and oxorhenium complexes, respectively. Compound 1 (M = (99)Tc, S = 4-methylthiophenol) crystallizes in the monoclinic space group P2(1)/a, a = 23.12(1) A, b = 14.349(6) A, c = 8.801(4) A, beta = 94.81(2) degrees, V = 2918(2) A(3), Z = 4. Compound 3 (M = Re, S = 4-methylthiophenol) crystallizes in the monoclinic space group P2(1)/a, a = 23.018(9) A, b = 14.421(5) A, c = 8.775(3) A, beta = 94.78(1) degrees, V = 2903(2) A(3), Z = 4. Compound 4 (M = Re, S = 4-methoxythiophenol) crystallizes in the orthorhombic space group Pbca, a = 16.32(1) A, b = 24.55(2) A, c = 16.94(1) A, V = 6788(9) A(3), Z = 8. In all cases, the coordination geometry around the metal is distorted octahedral with the equatorial plane being defined by the three sulfur atoms of the thiophenols and one nitrogen atom of 2,2'-bipyridine, while the apical positions are occupied by the second nitrogen atom of 2,2'-bipyridine and the oxygen of the M=O core. The complexes are stable, neutral, and lipophilic. Complete (1)H and (13)C NMR assignments are reported for all complexes. The analogous oxotechnetium complexes have been also synthesized at tracer level ((99m)Tc) by mixing the 2,2'-bipyridine and the corresponding thiol with Na(99m)TcO(4) generator eluate using NaBH(4) as reducing agent. Their structure was established by chromatographic comparison with authentic oxotechnetium and oxorhenium complexes using high performance liquid chromatography techniques.     

Is the nature of magnetic order in copper-oxides and in iron-pnictides different?

We use the results of first-principles electronic structure calculations and a strong coupling perturbation approach, together with general theoretical arguments, to illustrate the differences in super-exchange interactions between the copper-oxides and iron-pnictides. We provide a possible explanation for the two magnetic ground states within the same theoretical foundation. Contrary to the emerging view that magnetic order in the iron-pnictides is of itinerant nature, we argue that the observed magnetic moment is small because of frustration introduced by the electrons of the Fe orbitals as they compete to impose their preferred magnetic ordering.     

Parametric global optimisation for bilevel programming

We propose a global optimisation approach for the solution of various classes of bilevel programming problems (BLPP) based on recently developed parametric programming algorithms. We first describe how we can recast and solve the inner (follower’s) problem of the bilevel formulation as a multi-parametric programming problem, with parameters being the (unknown) variables of the outer (leader’s) problem. By inserting the obtained rational reaction sets in the upper level problem the overall problem is transformed into a set of independent quadratic, linear or mixed integer linear programming problems, which can be solved to global optimality. In particular, we solve bilevel quadratic and bilevel mixed integer linear problems, with or without right-hand-side uncertainty. A number of examples are presented to illustrate the steps and details of the proposed global optimisation strategy.     

A stimulus-responsive shape-persistent micelle bearing a calix[4]arene building block: reversible pH-dependent transition between spherical and cylindrical forms

A series of cationic calix[4]arene-based lipids with alkyl chains of varying length were newly synthesized, and the ones with propyl and hexyl tails, denoted by CaL[4]C3 and C6, respectively, were found to form spherical micelles at low pH (protonated state of the amine headgroup). Upon deprotonation with increasing pH, CaL[4]C3 showed a sphere-to-cylinder transition, while CaL[4]C6 changed from sphere, to cylinder, to monolayer vesicle. Synchrotron small-angle X-ray scattering (SAXS) patterns from both spherical and cylindrical CaL[4]C3 micelles exhibited a sharp intensity minimum, indicating shape monodispersity. The monodispersity of the CaL[4]C3 spherical micelles was further confirmed by analytical ultracentrifugation (AUC). SAXS, AUC, and static light scattering agreeingly indicated an aggregation number of 6. In contrast, CaL[4]C6 exhibited polydispersity with an average aggregation number of 12. When the number of carbons of the alkyl chain was increased to 9 (CaL[4]C9), cylinder formed at low pH, while at high pH, no clear morphology could be observed. The present results indicate that a very precise combination of tail length, head volume, and rigidity of the building block is required to produce shape-persistent micelles and that the shape-persistence can be maintained upon a structural transition. An attempt to reconstruct a molecular model for the spherical CaL[4]C3 micelle was made with an ab initio shape determining program.     

Experimental demonstration of 3×3 10 Gb/s reconfigurable free space optical card-to-card interconnects

In this Letter, we propose and demonstrate the concept of a free space optics-based parallel high-speed reconfigurable card-to-card interconnect architecture employing microelectromechanical systems (MEMS)-based steering mirror arrays in conjunction with VCSEL and photodiode arrays. A bit-error rate of ～10(-6) and a receiver sensitivity below -11.5 dBm are experimentally attained with a proof-of-concept 3×3 10 Gb/s reconfigurable card-to-card optical interconnect demonstrator.     

Ultra-broadband indoor optical wireless communication system with multimode fiber

In this paper we experimentally demonstrate an ultra-broadband indoor full-duplex WDM optical wireless communication system with multimode fiber. The multimode fiber is used because it is employed in most of the already installed in-building fiber distribution networks. Simultaneous error-free (BER<10(-9)) transmission of 4×12.5 Gbps downlink and 800 Mbps uplink has been successfully demonstrated. The experimental results show that, although the use of multimode fiber will induce ~2.4 cm reduction in the maximum error-free beam footprint in the downlink, the bit rate of the uplink can be much higher compared to the system with single-mode fiber.     

On the global solution of multi-parametric mixed integer linear programming problems

This paper deals with the global solution of the general multi-parametric mixed integer linear programming problem with uncertainty in the entries of the constraint matrix, the right-hand side vector, and in the coefficients of the objective function. To derive the piecewise affine globally optimal solution, the steps of a multi-parametric branch-and-bound procedure are outlined, where McCormick-type relaxations of bilinear terms are employed to construct suitable multi-parametric under- and overestimating problems. The alternative of embedding novel piecewise affine relaxations of bilinear terms in the proposed algorithmic procedure is also discussed.     

Composition and temperature dependence of cesium-borate glasses by molecular dynamics

The structural aspects of xCs2O-(1-x)B2O3 glasses have been investigated by molecular dynamics as functions of Cs2O content (x=0.2, 0.3, and 0.4) and temperature (T=300 and 1250 K). The tetrahedral (B?4-) and triangular (B?3,B?2O-, and B?O2 (2-)) short-range order borate units were found to be the structure-building entities of the simulated glasses [?=bridging oxygen (BO) and O-=nonbridging oxygen (NBO) atom]. The increase of Cs2O content results in the progressive increase of the NBO-containing triangle population at the expense of the BO4- tetrahedral units. The same effect is caused by temperature increase at a fixed Cs2O content, and this was associated with the "fragile" characteristics of alkali borate glasses. A comparison of simulated Cs and Li borates showed very similar structures at x=0.2, but dissimilar ones when the alkali content exceeds this composition. In particular, for x>0.2 Cs borates exhibit a preference for NBO formation relative to Li borates. Differences in the microstructure of sites hosting Cs ions were found, and this permits their classification into bridging (b type) and nonbridging type (nb type) of sites. b-type sites consist exclusively of BO atoms, while both BO and NBO atoms participate in nb-type sites. These differences in Cs-site local bonding characteristics were found to be reflected on the Cs-O(site) vibration frequencies. Also, the computed Cs-O vibrational responses for simulated Cs borates were found to compare well with experimental far-infrared spectra.     

A multi-parametric programming approach for constrained dynamic programming problems

In this work, we present a new algorithm for solving complex multi-stage optimization problems involving hard constraints and uncertainties, based on dynamic and multi-parametric programming techniques. Each echelon of the dynamic programming procedure, typically employed in the context of multi-stage optimization models, is interpreted as a multi-parametric optimization problem, with the present states and future decision variables being the parameters, while the present decisions the corresponding optimization variables. This reformulation significantly reduces the dimension of the original problem, essentially to a set of lower dimensional multi-parametric programs, which are sequentially solved. Furthermore, the use of sensitivity analysis circumvents non-convexities that naturally arise in constrained dynamic programming problems. The potential application of the proposed novel framework to robust constrained optimal control is highlighted.