Disulfide- and thiol-incorporating copper catenanes: synthesis, deposition onto gold, and surface studies

Two new copper-complexed [2]catenanes have been prepared, both of which consist of two different interlocking rings. In both cases, one of the rings incorporates a disulfide bridge. The other ring contains either a single chelate (phen=1,10-phenanthroline, a bidentate ligand) or two different chelates (phen and terpy, 2,2',6',2"-terpyridine, a tridentate chelate). Deposition of these two complexes on a gold electrode surface was carried out by standard procedures, leading to reductive cleavage of the S-S bridge. The adsorbed species can be viewed as [2]catenanes for which the gold atoms of the electrode surface are an integral fragment of one of the two rings. They yield clear electrochemical responses, but no motion is observed for the catenane incorporating a phen unit and a terpy fragment in one of the two rings, regardless of the metal oxidation state. This is at odds with the behavior of the parent compound in solution, which undergoes ring-gliding motions upon electrochemical reduction or oxidation of the copper center. Near-field microscopy was used to study the deposited layers (STM and AFM). STM images suggest that the molecules do not tend to order at long range on the surface. Polarization modulation-infrared reflection absorption spectroscopy (PM-IRRAS) led to promising results: the two catenanes deposited are likely to be oriented perpendicular to the gold surface. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2111/2002/f3636_s.pdf or from the author. 1: Infrared spectra of [Cu.2]+ as a powder (black line, transmission IR spectroscopy) and as a SAM on gold (dotted line, PM-IRRAS). (Spectra offset and scaled for clarity; significant peaks marked with an asterisk.) 2: STM image (819x819 nm2) of a monolayer of [Cu.3]+ on Au(111) on mica.     

Unusual effects in the pd-catalyzed asymmetric allylic alkylations: synthesis of chiral chromans

An examination of earlier reports of poor-to-modest results using Pd-catalyzed asymmetric allylic alkylations (AAA) to effect cyclization to form tetrasubstituted carbons reveals several novel factors that can influence this class of reactions. Thus, carboxylate has a major effect on such cyclizations wherein the ee increases from 14% ee favoring the S with no carboxylate to 84% ee favoring the R enantiomer in the presence of 1 equiv of carboxylate. Changing the double bond geometry from E to Z further increases the ee to 97%. Furthermore, the chiral catalyst that forms the R enantiomer with the E-alkene forms the S enantiomer with the Z alkene. In contrast to trisubstituted alkene substrates, disubstituted ones show a decrease in ee in going from the E to Z alkenes. The role of carboxylate appears to be a ligand to Pd during the catalytic cycle, a previously unsuspected phenomenon since such reactions are generally believed to involve pi-allylpalladium cationic complexes. The dependence upon alkene geometry helps define the nature of the chiral pocket which better accommodates a Z alkene compared to an E alkene. The results are compatible with the enantiodiscriminating step being ionization which occurs by coordination of the palladium to one of the two prochiral faces of the double bond. A synthesis of (+)-clusifoliol, a constituent of a folk medicine for treatment of malignant tumors, which also assigns the absolute configuration, illustrates the utility of the method.     

The Human Melanocyte as a Particular Target for UVA Radiation and an Endpoint for Photoprotection Assessment

The induction of DNA breaks by UVA (320-400 nm) in the nucleus of normal human melanocytes in culture was investigated using single cell gel electrophoresis, also called the comet assay. Endogenous pigment and/or melanin-related molecules were found to enhance DNA breakage: comets were more intense in melanocytes than in fibroblasts, in cells with high melanin content or after stimulation of melanogenesis by supplying tyrosine in the culture medium. After UVA doses where strong comets were observed, neither cytotoxicity nor stimulation of tyrosinase activity were detected. However, the accumulation of p53 protein suggested that cells reacted to genotoxic stress under these experimental conditions. The same approach was used to compare two sunscreens with identical sun protection factors but different UVA protection factors. The results presented in this paper suggest that human melanocytes may be used as a target cell to evidence broadspectrum photoprotection. Moreover, these data appear to be helpful in getting a better understanding of the role of sunlight in the initiating steps of melanocyte transformation.     

Credibility premiums for the zero-inflated Poisson model and new hunger for bonus interpretation

The purpose of this paper is to explore and compare the credibility premiums in generalized zero-inflated count models for panel data. Predictive premiums based on quadratic loss and exponential loss are derived. It is shown that the credibility premiums of the zero-inflated model allow for more flexibility in the prediction. Indeed, the future premiums not only depend on the number of past claims, but also on the number of insured periods with at least one claim. The model also offers another way of analysing the hunger for bonus phenomenon. The accident distribution is obtained from the zero-inflated distribution used to model the claims distribution, which can in turn be used to evaluate the impact of various credibility premiums on the reported accident distribution. This way of analysing the claims data gives another point of view on the research conducted on the development of statistical models for predicting accidents. A numerical illustration supports this discussion.     

Instability of mercury in specimens of human urine for external quality assessment

An under-recovery of inorganic mercury added to urine and a wide range of results is observed in quality assessment schemes (EQAS) for trace elements. Furthermore, the under-recoveries are inconsistent suggesting features associated with the urine matrix may make the mercury unavailable for measurement. To investigate the instability of mercury in urine the following experiments were set up: (1) a sample of Hg²⁺ in water with various ‘stabilizers’ added was sent to UK external quality assessment scheme participants. (2) Urine was collected from volunteers who also completed a 3-day food diary. Hg, Ca, Mg, Se, uric acid, phosphate, creatinine, reducing substances and protein were measured. Inorganic mercury was spiked into the urine, stabilizers were added and the mercury determined following storage. The results confirmed under-recovery of mercury in association with the urine matrix. Further investigations of how urinary components affect the measurement of mercury are necessary.     

Samarium diiodide-induced intramolecular pinacol coupling of dinitrones: synthesis of cyclic cis-vicinal diamines

Pinacol coupling of alkyl dinitrones mediated by SmI2 was achieved in the presence of a proton source allowing the synthesis of cyclic vicinal diamines with good cis-selectivity.     

Chain elongations by three carbon atoms at a time in the boron-catalyzed polymerization of methallyltriphenylarsonium ylide

Methallyltriphenylarsonium ylide polymerized in the presence of catalytic amounts of trialkylboranes. Linear polymers containing a terminal alcohol function were obtained after alkaline hydrogen peroxide oxidation. The chain of these polymers is constituted of methyl-substituted double bonds, separated by one methylene group. Their structure is related to that of natural rubber, in which the double bonds are separated by two methylene groups. These polymers arise from successive chain elongations of three carbon atoms at a time. A cyclic, polymeric ketone was also prepared from a cyclic trialkylborane. The mechanism, which involves a boratropic rearrangement after every insertion of a monomer, is discussed.     

Subdiffusion and dynamical heterogeneities in a lattice glass model

We study a kinetically constrained lattice glass model in which continuous local densities are randomly redistributed on neighboring sites with a kinetic constraint that inhibits the process at high densities, and a random bias accounting for attractive or repulsive interactions. The full steady-state distribution can be computed exactly in any space dimension d. Dynamical heterogeneities are characterized by a length scale that diverges when approaching the critical density. The glassy dynamics of the model can be described as a reaction-diffusion process for the mobile regions. The motion of mobile regions is found to be subdiffusive, for a large range of parameters, due to a self-induced trapping mechanism.     

The subtle nature of financial random walks

We first review the most important "stylized facts" of financial time series, that turn out to be, to a large extent, universal. We then recall how the multifractal random walk of Bacry, Muzy, and Delour generalizes the standard model of financial price changes and accounts in an elegant way for many of their empirical properties. In a second part, we provide empirical evidence for a very subtle compensation mechanism that underlies the random nature of price changes. This compensation drives the market close to a critical point, that may explain the sensitivity of financial markets to small perturbations, and their propensity to enter bubbles and crashes. We argue that the resulting unpredictability of price changes is very far from the neoclassical view that markets are informationally efficient.