Preparation of self-assembled fluorinated molecular aggregates, fluorescein nanocomposites: an extremely enhanced light absorption in nanocomposites

Self-assembled fluorinated molecular aggregates formed by fluoroalkyl end-capped N-(1,1-dimethyl-3-oxobutyl)acrylamide oligomers, N,N-dimethylacrylamide oligomers, and acrylic acid oligomers in methanol could selectively recognize fluoresceins as guest molecules to form a new class of fluorinated aggregates-fluorescein nanocomposites. These fluorinated fluorescein nanocomposites that are obtained exhibit an extraordinarily enhanced light absorption (_max ca. 440 nm) compared to that (_maxs 452, 480 nm) of the parent fluorescein in the absence of fluorinated aggregates.     

Photografting of polymers onto nanosized silica surface initiated by eosin moieties immobilized onto the surface

The photograft polymerization of various vinyl monomers onto nanosized silica surfaces was investigated. It was initiated by eosin moieties introduced onto the silica surface. The preparation of the silica with eosin moieties was achieved by the reaction of eosin with benzyl chloride groups on the silica surface.These were introduced by the reaction of surface silanol groups with 4‐(chloromethyl)phenyltrimethoxysilane in the presence of t‐butyl ammonium bromide as a phase‐transfer catalyst. The photopolymerization of various vinyl monomers, such as styrene, acrylamide, acrylic acid, and acrylonitrile was successfully initiated by eosin moieties on the silica surface in the presence of ascorbic acid as a reducing agent and by oxygen. The corresponding polymers were grafted from the silica surface. The grafting efficiency (percentage of grafted polymer to total polymer formed) in the photoinitiation system was much larger than that in the radical polymerization initiated by surface radicals; these radicals were formed by the thermal decomposition of azo groups introduced onto the silica surface. It was found that the polymer‐grafted silica gave stable dispersions in good solvents of grafted polymer and the wettability of the surfaces can be easily controlled by grafting of polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 600–606, 2005     

Liposomes possess drastic capabilities for topological transformation

Morphological and topological changes of biological membranes play essential roles in cellular activities. It has been thought that these transformations are made possible through interactions with proteins. However, direct observation of giant liposomes by optical dark-field microscopy reveals that the lipid bilayer itself possesses the ability to undergo topological transformation.     

Synthesis and evaluation of 1-arylsulfonyl-3-piperazinone derivatives as a factor Xa inhibitor II. Substituent effect on biological activities

Intravascular clot formation is an important event in a number of cardiovascular diseases. The prevention of blood coagulation has become a major target for new therapeutic agents. Factor Xa (FXa) is a trypsin-like serine protease that plays a key role in the blood coagulation cascade and represents an attractive target for anticoagulant drug development. We have investigated substituents in the central part of a lead compound (3: M55113), and discovered that compound M55551 (34: (R)-4-[(6-Chloro-2-naphthalenyl)sulfonyl]-6-oxo-1-[[1-(4-pyridinyl)-4-piperidinyl]methyl]-2-piperazinecarboxylic acid) is a potent inhibitor of FXa (IC(50)=0.006 microM), with high selectivity for FXa over trypsin and thrombin. The activity of this compound is ten times more powerful than the lead compound.     

New synthesis of multi-substituted α-chlorocyclobutanones from 1-chloro-3-cyanoalkyl p-tolyl sulfoxides by 4-Exo-Dig nucleophilic ring closure of magnesium carbenoids to nitrile group as the key reaction

1-Chloro-3-cyanoalkyl p-tolyl sulfoxides were easily prepared from 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from carbonyl compounds and chloromethyl p-tolyl sulfoxide, with lithium α-cyano carbanion of acetonitrile derivatives in good yields. Treatment of these sulfoxides with i-PrMgCl resulted in the formation of multi-substituted α-chlorocyclobutanones in good to high yields via the 4-Exo-Dig nucleophilic ring closure of the generated magnesium carbenoid intermediates to the nitrile group. This procedure provides a new and good way for the synthesis of multi-substituted α-chlorocyclobutanones from carbonyl compounds and substituted acetonitriles with formation of three carbon–carbon bonds in relatively short steps.     

Synthesis of Firefly Luciferin Analogues and Evaluation of the Luminescent Properties

Five new firefly luciferin ( 1 ) analogues were synthesized and their light emission properties were examined. Modifications of the thiazoline moiety in 1 were employed to produce analogues containing acyclic amino acid side chains ( 2 – 4 ) and heterocyclic rings derived from amino acids ( 5 and 6 ) linked to the benzothiazole moiety. Although methyl esters of all of the synthetic derivatives exhibited chemiluminescence activity, only carboluciferin ( 6 ), possessing a pyrroline‐substituted benzothiazole structure, had bioluminescence (BL) activity (λ_max=547 nm). Results of bioluminescence studies with AMP‐carboluciferin (AMP=adenosine monophosphate) and AMP‐firefly luciferin showed that the nature of the thiazoline mimicking moiety affected the adenylation step of the luciferin–luciferase reaction required for production of potent BL. In addition, BL of 6 in living mice differed from that of 1 in that its luminescence decay rate was slower.     

Interpolation and Sampling: E.T. Whittaker, K. Ogura and Their Followers

The classical sampling theorem has often been attributed to E.T.?Whittaker, but this attribution is not strictly valid. One must carefully distinguish, for example, between the concepts of sampling and of interpolation, and we find that Whittaker worked in interpolation theory, not sampling theory. Again, it has been said that K.?Ogura was the first to give a properly rigorous proof of the sampling theorem. We find that he only indicated where the method of proof could be found; we identify what is, in all probability, the proof he had in mind. Ogura states his sampling theorem as a ??converse of Whittaker??s theorem??, but identifies an error in Whittaker??s work. In order to study these matters in detail we find it necessary to make a complete review of the famous 1915 paper of E.T. Whittaker, and two not so well known papers of Ogura dating from 1920. Since the life and work of Ogura is practically unknown outside Japan, and there he is usually regarded only as an educationalist, we present a detailed overview together with a list of some 70 papers of his which we had to compile. K.?Ogura is presented in the setting of mathematics in Japan of the early 20th century. Finally, because many engineering textbooks refer to Whittaker as a source for the sampling theorem, we make a very brief review of some early introductions of sampling methods in the engineering context, mentioning H.?Nyquist, K.?Küpfmüller, V.?Kotel??nikov, H.?Raabe, C.E. Shannon and I.?Someya.     

Effects of mechanical rotation on spin currents

We study the Pauli-Schr?dinger equation in a uniformly rotating frame of reference to describe a coupling of spins and mechanical rotations. The explicit form of the spin-orbit interaction (SOI) with the inertial effects due to the mechanical rotation is presented. We derive equations of motion for a wave packet of electrons in two-dimensional planes subject to the SOI. The solution is a superposition of two cyclotron motions with different frequencies and a circular spin current is created by the mechanical rotation. The magnitude of the spin current is linearly proportional to the lower cyclotron frequency.