On catenate network formation by end-linking reactions

Catenate network formation by end-linking reactions of linear chains with bifunctional regents is studied theoretically and by computer simulations. It is found that the reaction cannot reach its stationary limit, and catenate networks are never formed by this method. An alternative method that will lead to catenate networks nearly in the topological equilibrium state is proposed. It is pointed out that catenate networks are an ideal system for studying the role of entanglement in rubber elasticity. © 1993 John Wiley & Sons, Inc.     

Cellular uptake and photocytotoxicity of glycoconjugated porphyrins in HeLa cells

Thirty-two glycoconjugated porphyrins were synthesized by a modification of Lindsey method in the presence of Zn(OAc)(2).2H(2)O as a template. The Zn(2+) ion template strategy improved the yield about three-fold in the case of meta-substituted tetraphenylporphyrins. In addition, free-base porphyrins were obtained almost quantitatively by demetalation with 4 M HCl. Sixteen deacetylated glycoconjugated porphyrins were tested as candidate photodynamic therapy (PDT) drugs using HeLa cells. Most of the deacetylated glycoconjugated porphyrins showed higher cellular uptake than tetraphenylporphyrin tetrasulfonic acid (TPPS), and 5,10,15,20-tetrakis[4-(beta-D-arabinopyranosyloxy)phenyl]porphyrin (p-5d) in particular showed 18.5-fold higher uptake than TPPS. The photocytotoxicity of 5,10,15,20-tetrakis[4-(beta-D-glucopyranosyloxy)phenyl]porphyrin (p-5a), p-5d and TPPS was examined with HeLa cells, using a light dose of 16 J/cm(2). These photosensitizers had no cytotoxicity in the dark, but their photocytotoxicity increased in the order of TPPS < p-5a < p-5d. These results suggest p-5d is a good candidate for a PDT drug.     

THE EFFECT OF LIGHT ON THE OCELLAR PIGMENT OF SPIROCODON, AN ANTHOMEDUSA

Abstract— The ocellar pigment of Spirocodon saltatrix was extracted with 2% mildly alkaline cetyltrimethylammonium bromide (CTAB) and 90% methanol acidified with HCl. In the case of CTAB-extracted pigment, maximum changes in optical density upon illumination occurred in mildly alkaline media under aerobic conditions and in neutral media under anaerobic conditions. The density spectrum of the sample illuminated under anaerobic conditions closely resembled that of the reduced form of the pigment illuminated in the presence of air. When reduced in darkness, the pigment became photostable and its density spectrum differed from that of the pigment reduced after illumination. On aeration of the pigment solution illuminated under anaerobic conditions, its density spectrum in the visible range became similar to that of the pigment illuminated in the presence of air. A trace of air dissolved in experimental media caused auto-oxidation of the reduced form, during the process of which a definite isosbestic point was observed at 480 mμ. Under anaerobic conditions, short period of illumination produced changes in spectral absorbance only in the visible range. Changes in the u.v. range required longer exposures. The pigment extracted with acidified methanol was readily auto-oxidizable and it was the reduced form which showed photosensitivity, though the degree of sensitivity was extremely low. The density spectrum of illuminated pigment resembled that of the oxidized form. From these experiments, a tentative scheme involving an electron transfer system has been suggested for the chain of photic reaction of the anthomedusan ocellar pigment.     

Radiochemical challenges in the study of endohedral fullerenes and MD simulation

The formation of atom-doped fullerenes has been investigated by using several types of radionuclides produced by nuclear reactions. From the trace of the radioactivities after high performance liquid chromatography (HPLC), it was found that formation of endohedral fullerenes (or heterofullerene) with small atoms (Be, Li), noble-gas atoms (Kr, Xe) and 4B–6B elements (Ge, As, Se, Sb, Te etc.) is possible by a recoil process following the nuclear reaction. In order to show the possibility of creating endohedral fullerenes by inserting a foreign atom with a suitably high kinetic energy into C₆₀, we have carried out large-scale ab initio molecular dynamics simulations on the basis of the all-electron mixed-basis approach with atomic orbitals and plane waves for Li, Be, N, O, Na, S, Cl, K, V, Cu, As, Se, Sb, Te, Kr, Xe. This revised version was published online in July 2006 with corrections to the Cover Date.     

Generalized diffusion equation of interacting brownian particles

Macroscopic behavior of a system of brownian particles interacting with each other through potential forces is described by a generalized diffusion equation (GDE) for the density of particles. The diffusion coefficient in the GDE is given by the generalized Stokes—Einstein relation and generally depends on the density. In the presence of long-range interactions, the GDE becomes non-local in space. When a Coulomb interaction exists, the GDE corresponds to an improvement of the Poisson—Boltzmann equation.     

Synthesis and properties of 3-arylcyclohepta[4,5]imidazo[1,2-a]-1,3,5-triazine-2,4(3H)-diones and related compounds: photo-induced autorecycling oxidation of some amines

Novel 3-phenyl- and 3-(4-nitrophenyl)cyclohepta[4,5]imidazo[1,2-a]-1,3,5-triazine-2,4(3H)-diones and the corresponding imino derivatives 5a,b and 6a,b were synthesized in modest to moderate yields by the abnormal and normal aza-Wittig reaction of 2-(1,3-diazaazulen-2-ylimino)triphenylphosphorane with aryl isocyanates and subsequent heterocyclization reaction with a second isocyanate. The related cationic compound, 1-methyl-3-phenylcyclohepta[4,5]imidazo[1,2-a]-1,3,5-triazine-2,4(3H)-dionylium tetrafluoroborate 7a, was also prepared. The electrochemical reduction of these compounds exhibited more positive reduction potentials as compared with those of the related compounds of 3,10-disubstituted cyclohepta[4,5]pyrrolo[2,3-d]pyrimidine-2,4(1H,3H)-dione systems. In a search of the oxidizing ability, compounds 5a, 6a, and 7a were demonstrated to oxidize some amines to give the corresponding imines in more than 100% yield under aerobic and photo-irradiation conditions, while even benzylamine was not oxidized under aerobic and thermal conditions at 100 °C. The oxidation reactions by cation 7a are more efficient than that by 5a and 6a. Quenching of the fluorescence of 5a was observed, and thus, the oxidation reaction by 5a probably proceeds via electron-transfer from amine to the excited singlet state of 5a. In the case of cation 7a, the oxidation reaction is proposed to proceed via formation of an amine-adduct of 7a and subsequent photo-induced radical cleavage reaction.     

Metal atom synthesis ofsyn(1-3-η-but-2-enyl)(η-buta-1,3-diene)(triethylphosphine)cobalt

Summary Cocondensation of buta-1,3-diene with cobalt vapor followed by addition of triethylphosphine gave a new complexsyn-Co(C₄H₇)(C₄H₆)(PEt₃) (1) in 43% yield. The reaction pathway leading to (1) was investigated by matrix isolation i.r. spectroscopy. The monodentate butadiene, which was found as a reaction intermediate in the –196 toca. 0° temperature range, rearranges into a -butenyl or bidentate butadiene. The reaction of (1) with bromoethane gave cycloocta-1,5-diene and 4-vinylcyclohex-1-ene in quantitative yield. Complex (1) catalyzes the cyclotrimerization of phenylacetylene to 1,3,5-triphenylbenzene.     

Optimal control of quantum non-Markovian dissipation: reduced Liouville-space theory

An optimal control theory for open quantum systems is constructed containing non-Markovian dissipation manipulated by an external control field. The control theory is developed based on a novel quantum dissipation formulation that treats both the initial canonical ensemble and the subsequent reduced control dynamics. An associated scheme of backward propagation is presented, allowing the efficient evaluation of general optimal control problems. As an illustration, the control theory is applied to the vibration of the hydrogen fluoride molecule embedded in a non-Markovian dissipative medium. The importance of control-dissipation correlation is evident in the results.