Glutathionyl transferase catalyzed addition of glutathione to COMC: a new hypothesis for antitumor activity

[reaction: see text] Data are presented indicating that the potent antitumor activity of 2-crotonyloxymethyl-(4R,5R,6R)-4,5,6-trihydroxy-2-cyclohexenone (COTC) and 2-crotonyloxymethyl-2-cyclohexenone (COMC) is not likely the result of glyoxalase I inhibition, as has long been assumed. An alternative hypothesis is presented, based on the finding that COMC is a substrate for human glutathionyl transferase, which produces a transient, highly electrophilic glutathionylated 2-exomethylenecyclohexanone that can covalently modify proteins and nucleic acids.     

Bifunctional, conjugated oligomers for orthogonal self-assembly: selectivity varies from planar substrates to nanoparticles

A diphenylacetylene containing two different end groups (isonitrile and thioacetate) was synthesized, showing that the chemistry used to install each end group is compatible with that of the others. The isonitrile group binds preferentially to platinum, and the thiol group binds preferentially to gold. However, the selectivity was different when nanoparticles were compared to planar substrates.     

The nu(CO) vibrational spectra of planar transition metal carbonyl clusters

The nu(CO) vibrational spectra of planar transition cluster carbonyls containing M(CO)(4) groups are studied. It is possible to anticipate qualitatively, both for the infrared and Raman, the band intensity changes associated with increasing metallic nature of the cluster. These enable a unification of the band patterns shown by the species reported. As for (idealized) spherical clusters, the spherical harmonic model (SHM), suitably modified, becomes of more general applicability as cluster size increases, although for smaller species the tensor harmonic model (THM) makes a contribution.     

Syntheses and characterization of two dioxygen-reactive dinuclear macrocyclic schiff-base copper(I) complexes

The dinuclear copper(I) complex [Cu(2)L(1)(CH(3)CN)(2)](ClO(4))(2) (1, L(1) = 3,6,9,17,20,23-hexaazatricyclo[23.3.1.1]triaconta-1(29),2,9,11(30),12(13),14,16,23,25,27-decaene) has been structurally characterized. As previously described, intramolecular ligand hydroxylation (at the aromatic ring) was observed when 1 was reacted with dioxygen. A stopped-flow analysis of the reaction of 1 with dioxygen under different conditions did not allow a "dioxygen intermediate" to be spectroscopically detected. Detailed NMR and electrochemical data on 1 are also presented and evaluated for the first time. No copper(II) complexes of L(1) could be characterized due to hydrolysis of the compounds. In contrast, complex 2-differing from 1 only in an increase in the size of the chelate rings-did not undergo intramolecular hydroxylation when it was oxidized. The crystal structure of 2 is also described.     

Application of the Spherical Harmonic Model to the ν(CO) Vibrational Spectra of Some Fe(CO)4 and M(CO)5 (M=Cr, W) Transition Metal Cluster Carbonyl Species

When the Fe(CO)₄ and M(CO)₅ (M=Cr, W) groups are co-ordinated in C_3v and C_4v fashion, respectively, in transition metal carbonyl cluster species they contain two sets of non-symmetry related carbonyl groups. In the application of the spherical harmonic model (SHM) to the interpretation of the infrared spectra of these compounds it proves necessary first to treat these as for a normal, isolated, M(CO)₄ or M(CO)₅ group and then apply the SHM. This recognition gives insights into the general application of the SHM.     

Asymmetric conditional volatility in international stock markets

Recent studies show that a negative shock in stock prices will generate more volatility than a positive shock of similar magnitude. The aim of this paper is to appraise the hypothesis under which the conditional mean and the conditional variance of stock returns are asymmetric functions of past information. We compare the results for the Portuguese Stock Market Index PSI 20 with six other Stock Market Indices, namely the SP 500, FTSE 100, DAX 30, CAC 40, ASE 20, and IBEX 35. In order to assess asymmetric volatility we use autoregressive conditional heteroskedasticity specifications known as TARCH and EGARCH. We also test for asymmetry after controlling for the effect of macroeconomic factors on stock market returns using TAR and M-TAR specifications within a VAR framework. Our results show that the conditional variance is an asymmetric function of past innovations raising proportionately more during market declines, a phenomenon known as the leverage effect. However, when we control for the effect of changes in macroeconomic variables, we find no significant evidence of asymmetric behaviour of the stock market returns. There are some signs that the Portuguese Stock Market tends to show somewhat less market efficiency than other markets since the effect of the shocks appear to take a longer time to dissipate.     

Cutting sequences, regular polygons, and the Veech group

We describe the cutting sequences associated to geodesic flow on regular polygons, in terms of a combinatorial process called derivation. This work is an extension of some of the ideas and results in Smillie and Ulcigrai’s recent paper, where the analysis was made for the regular octagon. It turns out that the main structural properties of the octagon generalize in a natural way.     

Ulam stability for a delay differential equation

We study the Ulam-Hyers stability and generalized Ulam-Hyers-Rassias stability for a delay differential equation. Some examples are given.