Extensional Σ-Spaces in Type Theory

Synthetic Domain Theory provides a setting for denotational semantics following Dana Scott's slogan domains as sets in which all functions are continuous. Several approaches can be found in the literature, but they are either model-dependent or if they use an axiomatic setting then not uniformly and not explicitly. We present a completely logical approach to Synthetic Domain Theory (SDT), axiomatizing (complete) Extensional PERs. On these grounds some basic domain theory is developed. Special attention is devoted to admissibility. The axiomatic approach is advantageous since it allows for easy formalization and comparison to other axiomatic settings.The consistency of the theory is shown by providing an appropriate realizability model. It is discussed how to get from this special kind of SDT {à la Scott} to a more general form which unifies several approaches.     

Capillary electrophoresis in anti-cancer metallodrug research: advances and future challenges

An efficient and convenient separation method has been a long sought after goal for anti-cancer metallodrug developers. For many reasons, capillary electrophoresis (CE) has recently emerged as the method of choice for the separation of intact platinum metal complexes and their metabolites, assessment of drug stability, and studying the interaction of the administered and potential tumor-inhibiting metallocomplexes with biomolecules. Due to the application of gentle separation conditions and successful developments in combinations with molecule-specific detectors, CE is also growing in importance as a versatile tool for the characterization of specific metal-bioligand binding products and thereby for providing mechanism-of-action information. Recent advances in metallodrug monitoring by CE are reviewed and critically evaluated. Likewise, the current limitations of CE in the field, such as the lack of assays involving individual proteins and targeting real-world biological samples, are brought into focus. Further strategies for method's refinement in anti-cancer metallodrug research that should ultimately take place along these lines and result in the development of high-throughput screening CE systems in the near future are finally discussed.     

High-performance liquid chromatography with diamond ATR–FTIR detection for the determination of carbohydrates,alcohols and organic acids in red wine

A horizontal diamond attenuated total reflection (ATR) element has been incorporated in a flow-through cell with low dead volume and used for on-line mid-IR detection in high-performance liquid chromatography. The chemical inertness of the ATR element permitted the use of a strongly acidic mobile phase in the isocratic separation. The hyphenation was used for the analysis of organic acids, sugars and alcohols in red wine. In the case of co-eluting analytes multivariate curve resolution-alternating least squares (MCR-ALS) was successfully employed for quantitative analysis.     

Chiral pyrimidine metallacalixarenes: synthesis, structure and host-guest chemistry

A set of enantiomerically pure cyclic multinuclear complexes with the formula cis-[a(2)PdL](n) (n+) [a(2)=(R,R)-1,2-diaminocyclohexane (R,R-dach), (S,S)-1,2-diaminocyclohexane (S,S-dach); n=4, 6; LH=2-hydroxypyrimidine (2-Hpymo), 4,6-dimethyl-2-hydroxypyrimidine (2-Hdmpymo) and 4-hydroxypyrimidine (4-Hpymo)] were obtained by reaction of cis-[a(2)Pd(H(2)O)(2)](2+) and LH in aqueous media. The polynuclear complexes were studied by (1)H NMR spectroscopy and X-ray crystallography. These studies revealed that the N1,N3-bridging mode exhibited by the pyrimidine moieties is ideally suited for formation of inorganic analogues of calixarenes (metallacalixarenes) in a self-assembly process. The most stable species are the tetranuclear metallacalix[4]arenes, which are obtained in all cases. Hexanuclear species, namely, [a(2)Pd(2-dmpymo)](6) (6+), were also isolated and fully characterised. (1)H NMR experiments show conversion of [a(2)Pd(2-dmpymo)](6) (6+) to [a(2)Pd(2-dmpymo)](4) (4+) on heating. Analogously to organic calixarenes, these systems are also capable of incorporating hard metal ions at the oxo surface. Additionally, investigations on the receptor properties of these metallacalixarenes towards mononucleotides showed that enantioselective recognition processes occur in aqueous media.     

Magnetic penetration depth of 585-01585-01585-01: Tc ∼ σ0 in the overdoped region

We report transverse field muon spin rotation experiments carried out on Tl₂Ba₂CuO₆₊. This system spans the whole overdoped regime, in which T_c is reduced by excess oxygen doping despite an increasing normal state carrier concentration. In the heavily overdoped regime the extrapolated low temperature depolarization rate(0) is found to scale linearly with the superconducting critical temperature T_c similar to the behavior previously observed for other cuprates in the underdoped regime. In the framework of the clean limit London model,(0) ^–2 n _s (0)/m _s ^* , suggesting that the depression of T_c by overdoping is associated with a decrease of the superconducting condensate density. This needs to be understood in view of the observed increase in the normal state carrier density. We discuss some possible explanations for this behavior.     

Cationic tetrakis(nucleobase)complexes of PtII as metalloligands and potential building blocks for molecular architectures

Three cationic tetrakis(nucleobase) complexes of Pt(II) have been synthesized: [Pt(Hmhyp-N7)4](NO3)2.H2O 1, [Pt(Hegua-N7)4](NO3)2.2KNO(3).5H2O and trans-[Pt(Hmcyt-N3)2(Hegua-N7)2](NO3)2 3 (Hmhyp = 9-methylhypoxanthine, Hegua = 9-ethylguanine, Hmcyt = 1-methylcytosine). The X-ray crystal structure of has been determined. All three cationic compounds rapidly react with Hg(II), but gel formation prevented an adequate characterization of the products formed. However, a Cu(II) adduct of was isolated in crystalline form and characterized crystallographically. [{(H2O)Cu(Hmhyp)4Pt}2Cu(ClO4)4)](ClO4)2(NO3)4.6H2O crystallizes in a centrosymmetric Cu-Pt-Cu-Pt-Cu chain structure with Cu-Pt separations of 2.791(1)A(outside) and 3.8980(9)A(inside). Two of the three Cu(II) ions are bound via exocyclic O(6) sites of the Hmhyp nucleobases. At neutral and moderate alkaline pH both and form virtually insoluble precipitates, which redissolve at strongly alkaline pH to give eventually anionic [Pt(L)4]2- species (L = mhyp, egua). Finally, interacts with complementary Hmcyt to give Watson-Crick associates, as demonstrated by 1H NMR spectroscopy in DMSO-d(6).