Kinetic and mechanistic investigation into the influence of chelate substituents on the substitution reactions of platinum(II) terpyridine complexes

The substitution kinetics of the complexes [Pt{4′‐(o‐CH₃‐Ph)‐terpy} Cl]SbF₆ (CH₃PhPtCl(Sb)), [Pt{4′‐(o‐CH₃‐Ph)‐terpy}Cl]CF₃SO₃ (CH₃PhPtCl(CF)), [Pt(4′‐Ph‐terpy)Cl]SbF₆ (PhPtCl), [Pt(terpy)Cl]Cl·2H₂O (PtCl), [Pt{4′‐(o‐Cl‐Ph)‐terpy}Cl]SbF₆ (ClPhPtCl), and [Pt{4′‐(o‐CF₃‐Ph)‐terpy}Cl]SbF₆ (CF₃PhPtCl), where terpy is 2,2′:6′,2″‐terpyridine, with the nucleophiles thiourea (TU), N,N′‐dimethylthiourea (DMTU), and N,N,N′,N′‐tetramethylthiourea (TMTU) were investigated in methanol as a solvent. The substitution reactions of the chloride displacement from the metal complexes by the nucleophiles were investigated as a function of nucleophile concentration and temperature under pseudo‐first‐order conditions using the stopped‐flow technique. The reactions followed the simple rate law k_obs = k₂[Nu]. The results indicate that the introduction of substituents in the ortho position of the phenyl group on the ancillary ring of the terpy unit does influence the extent of π‐backbonding in the terpy ring. This controls the electrophilicity of the platinum center, which in turn controls the lability of the chloro‐leaving group. The strength of the electron‐donating or ‐withdrawing ability of the substituents correlates with the reactivity of the complexes. Electron‐donating substituents decrease the rate of substitution, whereas electron‐withdrawing substituents increase the rate of substitution. This was supported by DFT calculations at the B3LYP/LACVP+** level of theory, which showed that most of the electron density of the HOMO is concentrated on the phenyl ligand rather than on the metal center in the case of the strongest electron‐withdrawing substituent in CF₃PhPtCl. The opposite was found to be true with the strongest electron‐donating substituent in CH₃PhPtCl. Thiourea was found to be the best nucleophile with N,N,N′,N′‐tetramethylthiourea being the weakest due to steric effects. The temperature dependence studies support an associative mode of activation. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 808–818, 2008     

Assessing the effects of homosexuals and bisexuals on the intrinsic dynamics of HIV/AIDS in heterosexual settings

A deterministic compartmental sex-structured HIV/AIDS model for assessing the effects of homosexuals and bisexuals on the intrinsic dynamics of the disease in heterosexual settings in which homosexuality and bisexuality issues have remained taboo is presented. The epidemic threshold and equilibria for the model are determined and stabilities are investigated. Comprehensive qualitative analysis of the model including invariance of solutions and permanence are carried out. The epidemic threshold known as the basic reproductive number suggests that heterosexuality, homosexuality, and bisexuality influence the growth of the epidemic in HIV/AIDS affected populations and the partial reproductive number (homosexuality induced or heterosexuality and bisexuality induced) with the larger value influences the overall dynamics of the epidemic in a setting. Numerical simulations of the model show that as long as one of the partial reproductive numbers is greater than unity, the disease will exist in the population. We conclude from the study that homosexuality and bisexuality enlarge the epidemic in a heterosexual setting. The theoretical study highlights the need to carry out substantial research to map homosexuals and bisexuals as it has remained unclear as to what extent this group has contributed to the epidemic in heterosexual settings especially in southern Africa, which has remained the epidemiological locus of the epidemic.     

Antiproton-neutron interactions at 100 GeV/c

From an exposure of the 30-inch deuterium filled bubble chamber to a 100 GeV/c antiproton-enriched beam at FNAL, we have calculated the topological cross sections for antiproton-neutron interactions with three or more charged particles in the final state. A comparison of our data with pn data at the same momentum allows us to estimate the annihilation contribution to each multiplicity, and hence calculate the average value, and width, of the annihilation multiplicity distribution. Our results are consistent with those from $\text{p}\text{p}$ data at 100 GeV/c, but depart from the trend of lower-energy $\text{p}\text{p}$ data.     

Off-shell effects in the (p, 2p) reaction

It is shown that, within the limitations of the distorted-wave off-shell impulse approximation, future accurate (p, 2p) experiments near 150 MeV incident energy can be helpful in distinguishing between some of six phenomenological nuclear potentials that are examined. On-shell differences between the Reid soft-core and five different one-boson-exchange potentials are amplified in the (p, 2p) context in such a way that an accurately measurable feature, the peak height ratio for 1p knockout, is sensitive to them.     

Graphical displays of acoustic properties of solids

The presentation of acoustic laws in diagrammatic form has found use in several ways, R12 particularly in determining acoustic quantities from elastic quantities, in choosing materials for line-line matching, and in tracing variations of properties with temperature.