Acidoswitchable NLO-phores: benzimidazolo[2,3-b]oxazolidines

This paper presents a series of acidoswitchable NLO-phores combining the 9-methylbenzimidazolo[2,3-b]oxazolidine core with various pi systems such as phenylethenyl, phenylethynyl, and naphthylethenyl. All the prepared derivatives are shown to display acidochromic behavior at ambient temperature. The remarkable contrast in the NLO response along the reversible transformations observed in HRS experiments is rationalized by high level theoretical calculations.     

Improved anti-inflammatory properties for naproxen with cyclodextrin-grafted polysaccharides

Mannan and carboxymethylcellulose, previously activated by periodate oxidation, were grafted with mono-6-butylenediamino-6-deoxy-beta-cyclodextrin derivatives by reductive alkylation in the presence of sodium borohydride. The formation of supramolecular complexes between these polymers and Naproxen was confirmed by fluorescence spectroscopy. The solubility of the drug was 3.8-4.6 fold increased in the presence of the cyclodextrin-grafted polysaccharides. The in vivo anti-inflammatory property of Naproxen was 1.7 times higher after supramolecular association with beta-cyclodextrin-branched mannan.     

Catalysts for monooxygenations made from polyoxometalate: an iron(V)-oxo derivative of the Lindqvist anion

This work uses density functional calculations to design a new high-valent Fe(V)=O catalyst [Mo5O18Fe=O]3-, which is based on the Lindqvist polyoxometalate (Mo6O19(2-)). Because the parent species is stable to oxidative conditions, one may assume that the newly proposed iron-oxo species will be stable, too. The calculated M?ssbauer spectroscopic data may be helpful toward an eventual identification of the species. The calculations of C-H hydroxylation and C=C epoxidation of propene show that, if made, [Mo5O18Fe=O]3- should be a potent oxidant that will be subject to strong solvent effect. Moreover, the Lindqvist catalyst leads to an intriguing result; the reaction that starts along an epoxidation pathway with C=C activation ends with a C-H hydroxylation product ((4)6) due to rearrangement on the catalyst. The origins of this result are analyzed in terms of the structure of the catalyst and the electronic requirements for conversion of an epoxidation intermediate to a hydroxylation product. Thus, if made, the [Mo5O18Fe=O]3 will be a selective C-H hydroxylation reagent.     

Ru(TAP)3]2+-photosensitized DNA cleavage studied by atomic force microscopy and gel electrophoresis: a comparative study

Topological modifications of plasmid DNA adsorbed on a variety of surfaces were investigated by using atomic force microscopy (AFM). On mica modified with 3-aminopropyltriethoxysilane (APS) or poly-L-lysine, the interaction between the plasmid DNA and the surface "freezes" the plasmid DNA conformation deposited from solution, and the AFM images resemble the projection of the three-dimensional conformation of the plasmid DNA in solution. Modified mica with low concentrations of Mg(2+) leads to a decrease in the interaction strength between plasmid DNA and the substrate, and the AFM images reflect the relaxed or equilibrium conformation of the adsorbed plasmid DNA. Under these optimized deposition conditions, topological modifications of plasmid DNA were produced under irradiation in the presence of [Ru(TAP)(3)](2+) (TAP = 1,4,5,8-tetraazaphenanthrene), which is a non-intercalating complex, and were followed as a function of illumination time. The observed structural changes correlate well with the conversion of the supercoiled covalently closed circular form (ccc form) into the open circular form (oc form), induced by a single-strand photocleavage. The AFM results obtained after fine-tuning of the plasmid DNA-substrate interaction compare well with those observed from gel electrophoresis, indicating that under the appropriate deposition conditions, AFM is a reliable technique to investigate irradiation-induced topological changes in plasmid DNA.     

An efficient proton-coupled electron-transfer process during oxidation of ferulic acid by horseradish peroxidase: coming full cycle

Quantum mechanics/molecular mechanics calculations were utilized to study the process of oxidation of a native substrate (ferulic acid) by the active species of horseradish peroxidase (Dunford, H. B. Heme Peroxidases; Wiley-VCH: New York, 1999), Compound I and Compound II, and the manner by which the enzyme returns to its resting state. The results match experimental findings and reveal additional novel features. The calculations demonstrate that both oxidation processes are initiated by a proton-coupled electron-transfer (PCET) step, in which the active species of the enzyme participate only as electron-transfer partners, while the entire proton-transfer event is being relayed from the substrate to and from the His42 residue by a water molecule (W402). The reason for the observed (Henriksen, A; Smith, A. T.; Gajhede, M. J. Biol. Chem. 1999, 274, 35005-35011) similar reactivities of Compound I and Compound II toward ferulic acid is that the reactive isomer of Compound II is the, hitherto unobserved, Por(*)(+)Fe(III)OH isomer that resembles Compound I. The PCET mechanism reveals that His42 and W402 are crucial moieties and they determine the function of the HRP enzyme and account for its ability to perform substrate oxidation (Poulos, T. L. Peroxidases and Cytochrome P450. In The Porphyrin Handbook; Kadish, K. M., Smith, K. M., Guilard, R., Eds.; Academic Press: New York, 2000; Vol. 4, pp 189). In view of the results, the possibility of manipulating substrate oxidation by magnetic fields is an intriguing possibility.     

How does adhesion induce the formation of telephone cord buckles?

Compressively stressed thin films with low adhesion frequently buckle and delaminate simultaneously into telephone cords. Although these buckles have been studied for decades, no complete understanding of their propagation has so far been presented. In this study, we have coupled a nonlinear plate deformation with a cohesive zone model to simulate the kinematics of a propagating telephone cord buckle in very close agreement with experimental observations. Proper inclusion of the dependence of an adhesion upon the mode mixity proved to be central to the success of the approach. The clarification of the mechanism promises better understanding of buckle morphologies.     

Acoustic rotational manipulation using orbital angular momentum transfer

We report on the first quantitative test of acoustic orbital angular momentum transfer to a sound absorbing object immersed in a viscous liquid. This is done by realizing an original experiment that is to spin a millimeter-size target disk using an ultrasonic vortex beam. We demonstrate the balance between the acoustic radiation torque calculated from the Brillouin stress tensor and the viscous torque evaluated from the steady state spinning frequency. Moreover, we unveil a rotational acoustic streaming phenomenon that results from the acoustic angular momentum transfer to the host fluid. We show that it lowers the viscous torque, thereby restoring the torque balance.     

Self-induced nonlinear spin-orbit interaction of light in liquid crystals

We report on the observation of self-induced nonlinear spin-orbit interaction of light driven by Kerr orientational optical nonlinearities in liquid crystals. It consists of the self-induced spin-to-orbital nonlinear conversion for the angular momentum of light. The optical angular momentum conversion is driven by the creation of a topological liquid crystal defect by the light itself. Moreover, we show that such a nonlinear process can be significantly enhanced by using additional electric fields.     

Biodegradable polyphosphazenes for drug delivery

Polyphosphazene derivatives having amino acid ester side groups were prepared by reaction of poly(dichlorophosphazene) with ethyl esters of amino acids. The in vitro degradation studies demonstrated that the rate of degradation depends on the nature of the amino acids. Introducing small amounts of hydrolytically sensitive groups such as depsipeptide ester or hydrolysis-catalysing moieties, such as histidine ethyl ester co-substituents, resulted in an increase of the degradation. The rate of hydrolytic degradation of the polyphosphazene material could be controlled by the content of the hydrolytically sensitive side groups or by blending hydrolysis-sensitive polymers with more stable derivatives. The results obtained from the in vivo implantation of biodegradable polyphosphazenes in mice indicate that the materials are very well tolerated by the animal body. Biodegradable polyphosphazenes have been used as matrix for the design of drug delivery systems. The rate of the in vitro release of mitomycin C from biodegradable polyphosphazenes can be controlled by changing the chemical composition of the polymer or by blending polymers of different chemical compositions.     

Polymeric prodrugs of mitomycin C

Poly-[N-(2-hydroxyethyl)-L-glutamine] (PHEG) prodrugs of the cytotoxic agent Mitomycin C were synthesized using peptidyl spacers to link the drug to the polymeric carrier. The influence on the length and detailed structure of the oligopeptide on the rate of drug release was investigated in buffer, in the presence of lysosomal enzymes (tritosomes, cathepsin B and D) and metalloprotease type IV collagenase. It was observed that tetra- and hexapeptide based conjugates generally release Mitomycin C (MMC) more effectively than tripeptide derivatives. The gly-phe-ala-leu conjugate released MMC very rapidly both in presence of lysosomal enzymes and collagenase IV. Only in the presence of the aspartic protease cathepsin D, the gly-phe-leu-gly-phe-leu derivative turned out to be a better substrate. In vivo studies against C26 solid tumour bearing mice suggest that PHEG-spacer-MMC conjugates act as prodrugs of MMC: antitumour efficacy of the macromolecular prodrugs was better than free MMC both in inhibition of tumour growth and increasing survival.