Structural architectures of charge-assisted,hydrogen-bonded, 2D layered amine⋯tetraphosphonate and zinc⋯tetraphosphonate ionic materials

The synthesis, characterization and structural analyses of ionic amine-phosphonate and hydrated metal ion-phosphonate compounds are reported. These are (en)(HDTMP), (NH₄)(EDTMP), Zn(H₂O)₆(TDTMP) (en = ethylenediamine, HDTMP = hexamethylenediamine-tetrakis(methylenephosphonate), EDTMP = diethylenediamine-tetrakis(methylenephosphonate), TDTMP = tetramethylenediamine-tetrakis(methylenephosphonate)). All three compounds are composed of discrete anions and cations, stabilized by intricate networks of hydrogen bonds, and form 2D layered architectures.     

Rheology of Ziegler–Natta and metallocene high-density polyethylenes: broad molecular weight distribution effects

The linear viscoelastic properties of two series of Ziegler–Natta and metallocene HDPEs (ZN-HDPEs and m-HDPEs, respectively) of broad molecular weight distribution (MWD) have been studied. Correlations between zero-shear viscosity and molecular weight and molecular weight distribution show that the breadth of the MWD for m-HDPEs plays a role. Other interesting correlations between the crossover modulus and steady-state compliance with MWD of both these classes of polymers have also been derived. Finally, the steady-shear viscosities from capillary rheometry are compared with LVE data to check the applicability of the empirical Cox–Merz rule. It is shown that the original Cox–Merz rule is applicable for the ZN-HDPEs, while it apparently fails for the m-HDPEs. However, once the capillary data for m-HDPEs are corrected for slip effects, the applicability of the Cox–Merz rule is validated for their case as well.     

Microfabricated disposable lab-on-a-chip sensors with integrated bismuth microelectrode arrays for voltammetric determination of trace metals

This work reports the fabrication of disposable three-electrode cells with integrated metal-film electrodes. The devices were fabricated by a multi-step micro-fabrication approach combining sputtering for the deposition of metals and the dielectric material (SiO₂) on the surface of a silicon wafer and photolithography for the definition of the geometry of the sensors. The working electrode was a microelectrode array consisting of bismuth microdisks while the reference and counter electrode strips were made of Ag and Pt, respectively. The utility of these devices was tested for the trace determination of Pb(II) and Cd(II) by anodic stripping voltammetry and Ni(II) by adsorptive stripping voltammetry. The detection of these trace metals was carried out in unstirred and undeoxygenated solutions exhibiting sub-μg L⁻¹ limits of detection and enhanced analytical characteristics compared to conventional bismuth-film electrodes.     

Interaction of Metal Complexes with G‐Quadruplex DNA

Guanine‐rich sequences of DNA can assemble into tetrastranded structures known as G‐quadruplexes. It has been suggested that these secondary DNA structures could be involved in the regulation of several key biological processes. In the human genome, guanine‐rich sequences with the potential to form G‐quadruplexes exist in the telomere as well as in promoter regions of certain oncogenes. The identification of these sequences as novel targets for the development of anticancer drugs has sparked great interest in the design of molecules that can interact with quadruplex DNA. While most reported quadruplex DNA binders are based on purely organic templates, numerous metal complexes have more recently been shown to interact effectively with this DNA secondary structure. This Review provides an overview of the important roles that metal complexes can play as quadruplex DNA binding molecules, highlighting the unique properties metals can confer to these molecules.     

Spacetime Topology from the Tomographic Histories Approach: Part II

As an inverse problem, we recover the topology of the effective spacetime that a system lies in, in an operational way. This means that from a series of experiments we get a set of points corresponding to events. This continues the previous work done by the authors. Here the relativistic case is considered. The existence of upper bound in the speed of transfer of matter and information induces a partial order on the set of events. While the actual partial order is not known in our operational set up, the grouping of events to (unordered) subsets corresponding to possible histories, is given. From this we recover the partial order up to certain ambiguities that are then classified. Finally two different ways to recover the topology are sketched and their interpretation is discussed.     

Glafka-2004: Categorical Quantum Gravity

A synopsis-cum-update of work in the past half-decade or so on applying the algebraico-categorical concepts, technology and general philosophy of Abstract Differential Geometry (ADG) to various issues in current classical and quantum gravity research is presented. The exposition is mainly discursive, with conceptual, interpretational and philosophical matters emphasized throughout, while their formal technical-mathematical underpinnings have been left to the original papers. The general position is assumed that Quantum Gravity is in need of a new mathematical, novel physical concepts and principles introducing, framework in which old and current problems can be reformulated, readdressed and potentially retackled afresh. It is suggested that ADG can qualify as such a theoretical framework.Paper version of a talk given at the Glafka–2004: Iconoclastic Approaches to Quantum Gravity international theoretical physics conference, held in Athens, Greece (summer 2004).     

Experimental and theoretical Mössbauer study of an extended family of [Fe8(μ4-O)4(μ-4-R-px)12X4] clusters

Six [Fe(8)(μ(4)-O)(4)(μ-4-R-pyrazolato)(12)X(4)] complexes containing an identical Fe(8)(μ(4)-O)(4) core have been structurally characterized and studied by M?ssbauer spectroscopy. In each case, an inner μ(4)-O bridged Fe(III) cubane core is surrounded by four trigonal bipyramidal iron centers, the two distinct sites occurring in a 1:1 ratio. The M?ssbauer spectrum of each of the clusters consists of two quadrupole doublets, which, with one exception (X = NCS, R = H), overlap to give three absorption lines. The systematic variation of X and R causes significant changes in the M?ssbauer spectra. A comparison with values for the same clusters computed using density functional theory allows us to establish an unequivocal assignment of these peaks in terms of a nested model for the overlapping doublets. The changes in M?ssbauer parameters (both experimental and computed) for the 1-electron reduced species [Fe(8)(μ(4)-O)(4)(μ-4-Cl-pyrazolato)(12)Cl(4)](-) are consistent with a redox event that is localized within the cubane core.     

On the Hopficity of HNN-Extensions of Polycyclic Groups

For a group G, an HNN-extension of polycyclic groups, we give two necessary and sufficient conditions for G to be hopfian. One is based on the nature of the endomorphism of G and the other on the nature of the associated subgroups of G. At the end, we give an application for HNN-extensions of nilpotent groups.     

Relative response of TL and component-resolved OSL to alpha and beta radiations in annealed sedimentary quartz

Knowledge of the relative luminescence response to alpha and beta radiation is very important in TL and OSL dating. In the present study the relative alpha to beta response is studied in a sedimentary quartz sample, previously fired at 900 °C for 1 h, in the dose region between 1 and 128 Gy, for both thermoluminescence (TL) and linearly modulated optically stimulated luminescence (LM – OSL). The LM – OSL measurements were performed at room temperature and at 125 °C. All OSL signals were deconvolved into their individual components. Comparison of OSL curves after alpha and beta irradiation strongly supports that quartz OSL components follow first order kinetics in both cases. In the case of TL, the relative alpha to beta response is found to be very different for each TL glow-peak, but it does not depend strongly on irradiation dose. In the case of LM – OSL measurements, it is found that the relative behaviour of the alpha to beta response is different for three distinct regions, namely the fast OSL component, the region of medium OSL component originating from the TL glow-peak at 110 °C when stimulation takes place at room temperature and finally the region of slow OSL component. Following stimulation at ambient temperature, the relative alpha to beta response of all components was not observed to depend significantly on dose, with the value of ratio being 0.03 and a tendency to decrease with increasing dose. However, in the case of measurements performed at 125 °C, the relative response of the fast components is much enhanced, and for the remaining components it increases with increasing dose. Special care must be taken to examine the relative alpha to beta response of the fast component at 125 °C which contrasts the relative response of the TL peak at ca. 325 °C. The implications for the dating of annealed quartz are also briefly discussed.     

Wall slip and melt fracture of poly(lactides)

The wall slip and melt fracture behaviour of several commercial polylactides (PLAs) as well as their rheological properties under shear and extensional have been investigated. The PLAs have had weight-average molecular weights in the range of 10⁴–10⁵ g/mol and studied in the temperature range of 160–200°C. The solution properties and linear viscoelastic behaviour of melts indicate linear microstructure behaviour. PLAs with molecular weights greater than a certain value were found to slip, with the slip velocity to increase with decrease of molecular weight. The capillary data were found to agree well with linear viscoelastic envelope once correction for slip effects was applied. The onset of melt fracture for the high molecular weight PLAs was found to occur at about 0.2 to 0.3 MPa, depending on the geometrical characteristics of the dies and independent of temperature. Addition of 0.5 wt.% of a polycaprolactone (PCL) into the PLA that exhibits melt fracture was found to be effective in eliminating and delaying the onset of melt fracture to higher shear rates. This is due to significant interfacial slip that occurs in the presence of PCL.