Mild Synthesis of Amino‐Poly(ethylene glycol)s. Application to Steric Stabilization of Clays

The hydroxyl end groups of poly(ethylene glycol) (PEG) have been transformed easily and quantitatively into amino groups via the Mitsunobu reaction. Phthalimide was alkylated with PEGs and the hydrazinolysis of the resulting phthalimido‐PEGs gave the amino compounds in high yields. Quaternization of the amino groups leads to hydrophilic polymer chains bearing a positive charge on one or two ends, depending on the chosen PEG. Such products can be used to protect sterically, negatively charged particles such as clays.

     

Identification of Apigenin Metabolites in Rat Liver Perfusate by Column Switching High Performance Liquid Chromatography/Electrospray Ionization Mass Spectrometry

Summary.  A selective column switching high performance liquid chromatographic method has been used for the simultaneous determination of apigenin and metabolites in rat liver perfusate. This new method clearly separated apigenin and the metabolites with high resolution. The structures of metabolites were proposed based on selective ion recording and full scan analysis by electrospray ionization mass spectrometry. Corresponding author. E-mail: basly@pharma.unilim.fr Received May 15, 2002; accepted (revised) September 13, 2002     

Metal-chelating nanoparticles as selective fluorescent sensor for Cu2+

A fluorescent sensor for Cu(2+) at the nanomolar level in water has been designed by associating a BODIPY fluorophore and a selective ligand (cyclam) in ultrafine polymer nanoparticles.     

Chiralization in mesogenic 1,3-diacylaminobenzenes

The effect of molecular chirality in thermotropic mesomorphic H-bonded polymeric systems has not really been investigated so far. Therefore, five new chiral mesogenic diamides have been prepared and described. Besides more ordered mesophases, the enantiomers exhibit a chiral nematic polymorphism detected by microcalorimetry and probably corresponding to different modes of chiral coiling to give these singular twisted nematic phases.     

Influence of the Metal Ion on the Two‐Photon Absorption Properties of Lanthanide Complexes Including Near‐IR Emitters

The synthesis of tris(2‐thenoyltrifluoroacetonate)lanthanide(III) complexes featuring a diethylaminostyryl‐2,2′‐bipyridine coligand was achieved for lanthanum; the near‐infrared (NIR) emitters neodymium, erbium, and ytterbium; and the transition‐metal yttrium. The photophysical properties were thoroughly studied, and it was demonstrated that the conjugated bipyridine ligand acts as a good antenna for the sensitization of the NIR emitters. The two‐photon absorption (TPA) properties of all five complexes were investigated by using both two‐photon excited fluorescence and the Z‐scan method. We demonstrate that the nature of the rare earth ion has almost no influence on the TPA properties centered on the conjugated bipyridyl ligand. Finally, we show that Yb^III is sensitized by a two‐photon antenna effect, and that Nd^III is mostly sensitized by a one‐photon process involving direct excitation of forbidden f–f transitions.     

Charge-Transfer versus Charge-Separated Triplet Excited States of [ReI(dmp)(CO)3(His124)(Trp122)]+ in Water and in Modified Pseudomonas aeruginosa Azurin Protein

A computational investigation of the triplet excited states of a rhenium complex electronically coupled with a tryptophan side chain and bound to an azurin protein is presented. In particular, by using high-level molecular modeling, evidence is provided for how the electronic properties of the excited-state manifolds strongly depend on coupling with the environment. Indeed, only upon explicitly taking into account the protein environment can two stable triplet states of metal-to-ligand charge transfer or charge-separated nature be recovered. In addition, it is also demonstrated how the rhenium complex plus tryptophan system in an aqueous environment experiences too much flexibility, which prevents the two chromophores from being electronically coupled. This occurrence disables the formation of a charge-separated state. The successful strategy requires a multiscale approach of combining molecular dynamics and quantum chemistry. In this context, the strategy used to parameterize the force fields for the electronic triplet states of the metal complex is also presented.     

STRUCTURE-ACTIVITY STUDIES OF PHOTOACTIVATED ANTIVIRAL AND CYTOTOXIC TRICYCLIC THIOPHENES

The photoactivated antiviral and cytotoxic activities of the naturally occurring thiophene, alpha-terthienyl (1), and 15 synthetic analogues were evaluated against murine cytomegalovirus and Sindbis virus, and murine mastocytoma cells. After irradiation with near UV light, alpha-terthienyl and most of its analogues had significant toxicity, with minimum inhibitory concentrations in the range of 0.02-40 microM. In the absence of near UV irradiation, only one analogue had antiviral activity and five were cytotoxic. The most active analogues were those containing carboxylic acid, hydroxyl, or cyano substituents. Quantitative structure-activity relationship analysis of thiophene phototoxicity suggested that the rate of singlet oxygen production is the primary determinant of antiviral and cytotoxic activities. For phototoxicity against murine cytomegalovirus, a significant role for hydrophobicity was also demonstrated. Tricyclic thiophenes show significant potential for photochemotherapy of viral infections and cancer, and further evaluation in animal models is recommended.     

Bivariate Gonarov polynomials and integer sequences

Univariate Gonarov polynomials arose from the Gonarov interpolation problem in numerical analysis.They provide a natural basis of polynomials for working with u-parking functions,which are integer sequences whose order statistics are bounded by a given sequence u.In this paper,we study multivariate Gonarov polynomials,which form a basis of solutions for multivariate Gonarov interpolation problem.We present algebraic and analytic properties of multivariate Gonarov polynomials and establish a combinatorial relation with integer sequences.Explicitly,we prove that multivariate Gonarov polynomials enumerate k-tuples of integers sequences whose order statistics are bounded by certain weights along lattice paths in Nk.It leads to a higher-dimensional generalization of parking functions,for which many enumerative results can be derived from the theory of multivariate Gonarov polynomials.     

Goal achieving probabilities of cone‐constrained mean‐variance portfolios

In this paper, we establish closed‐form formulas for key probabilistic properties of the cone‐constrained optimal mean‐variance strategy, in a continuous market model driven by a multidimensional Brownian motion and deterministic coefficients. In particular, we compute the probability to obtain to a point, during the investment horizon, where the accumulated wealth is large enough to be fully reinvested in the money market, and safely grow there to meet the investor's financial goal at terminal time. We conclude that the result of Li and Zhou [Ann. Appl. Prob., v.16, pp.1751–1763, (2006)] in the unconstrained case carries over when conic constraints are present: the former probability is lower bounded by 80% no matter the market coefficients, trading constraints, and investment goal. We also compute the expected terminal wealth given that the investor's goal is underachieved, for both the mean‐variance strategy and the aforementioned hybrid strategy where transfer to the money market occurs if it allows to safely achieve the goal. The former probabilities and expectations are also provided in the case where all risky assets held are liquidated if financial distress is encountered. These results provide investors with novel practical tools to support portfolio decision‐making and analysis. Copyright © 2013 John Wiley & Sons, Ltd.     

An O(n log n) algorithm for finding all repetitions in a string

Any nonempty string of the form xx is called a repetition. An O(n log n) algorithm is presented to find all repetitions in a string of lenght n. The algorithm is based on a linear algorithm to find all the new repetitions formed when two strings are concatenated. This linear algorithm is possible because new repetitions of equal length must occur in blocks with consecutive starting positions. The linear algorithm uses a variation of the Knuth-Morris-Pratt algorithm to find all partial occurrences of a pattern within a text string. It is also shown that no algorithm based on comparisons of symbols can improve O(n log n). Finally, some open problems and applications are suggested.