Metalloporphyrin heterodimers,molecular bilayer fibers and monolayer leaflets

Amphiphilic metalloporphyrins assemble in water to form supramolecular fibers, which have been characterized by transmission electron microscopy. Loose octopus porphyrin fibers can be doped with hydrophobic electron acceptors, metalloporphyrin monomolecular sheets are crystalline. Charge separation occurs in amino porphyrin fibers without added electron acceptors. Bolaamphiphilic porphyrins with four pyridinyl or methyl pyridinium groups in β-pyrrolic positions have been synthesized. The regioisomer mixture is very soluble in water (≌ 0.1 M) and is ideally suited to form heterodimers with negatively charged ms-tetrasubstituted porphyrins. Bimetallic porphyrinate pairs are described. The zinc complex is stable down to pH 1.0. Regioisomer II forms well-defined molecular monolayer leaflets in bulk water at pH 2.5. The surface structure of such monolayers is discussed. It consists of a large cationic plane and hydrophobic edges. Possible applications are discussed shortly.     

Slow motion, trapping, and sorting of water- and chloroform-soluble porphyrins in nanowells

A two-step self-assembly procedure on smooth, aminated silica particles established holey monolayers. At first, single, flat-lying porphyrin tetraamides (A) were bound covalently, followed by the build-up of a rigid monolayer made of diamido bolaamphiphiles (bolas) around the porphyrin islands. "Nanowells" around porphyrin (A) bottoms with a uniform diameter of 2.2 nm and varying depths of 0.6, 1.0, or 1.5 nm depending on the length of the applied bolas were thus obtained. Oligoethylene headgroups solubilized the particles in water, ethanol, and chloroform/ethanol, and two hydrogen bond chains between the secondary amide groups prevented swelling of the monolayer. Manganese(III) porphyrinates (B) migrated from the bulk solution to the bottom of the form-stable nanowells with a speed of about 1 pm/s and were trapped there above porphyrin (A). After isolation of the (A,B) particles by centrifugation or ultrafiltration, the particles were suspended in a chloroform solution of a chlorin (C), which was also fixated irreversibly on the bottom of the nanowells. The nanowells thus contained three different porphyrins A,B,C in a noncovalent stack. The reverse sequence A,C,B was built-up correspondingly, first in chloroform/ethanol, and then in water. The "sorting" of A,B,C and A,C,B systems was characterized by visible spectra, sequence-dependent fluorescence quenching, and cyclic voltammetry of the top component. The molecular sorting method is the first of its kind and should be generally useful for the production of noncovalent reaction systems on any smooth surface.     

Raman and resonance-Raman spectra of CsI/I−3

Raman and resonance-Raman spectra of the I^?₃ ion isolated within CsI crystals have been studied using 647 nm and 488 nm exciting radiation. Sample temperatures between 300 and 20 K have been used. Eleven overtones of the symmetric stretching mode (nν₁) have been observed in the resonance-Raman spectrum excited by the 488 nm Ar⁺ laser line. Bands centred at 153, 170, 264 and 304 cm^?1 have been assigned as ν₃, 2ν₂, ν₁+ν₃ and 2ν₃(Σ⁺) respectively. The remaining structure between the nν₁ lines has been assigned as due to combinations of these lines with the lattice vibrations of the CsI crystal.     

Semileptonic (Λ b → Λcev) decay in a field theoretic quark model

The semileptonic decay width of heavy baryons such as (Λ _b → Λcev) has been estimated in the framework of a nonrelativistic field theoretic quark model where four component quark field operators along with a harmonic oscillator wave function are used to describe translationally invariant hadronic states. The present estimation does not make an explicit use of heavy quark symmetry and has a reasonable agreement with the experimentally measured decay width, polarisation ratio and form factors with the harmonic oscillator radii and quark momentum distribution inside the hadron as free parameters.     

Polymeric porphyrin and metalloporphyrin assemblies in bulk solution

Some water-soluble porphyrins aggregate in aqueous media to form fibrous assemblies. When polynucleotides are used as matrices, porphyrin monomers are aligned at the periphery or intercalated. Porphyrin-porphyrin interactions hardly occur. Metal-metal or metal-ligand-metal interactions have been observed in oxo-oligomers, pyrazine-bridged dimers and radical dimers. β-Substituted metallo-porphyrins, however, form no polymers. The only linear polymerization, which has so far been observed in molecular asemblies, occurs with amphiphilic porphyrin amides, amines and carboxylates and their metal complexes in water and of bacteriochlorophyll in DMF/water. These compounds form long-lived high molecular weight micellar, inverse micellar and vesicular fibers spontaneously in aqueous media. The porphyrin fibers in water are about 4-6 nm thick and up to several of μm long.     

Spectral Properties of the Cauchy Operator and Its Product with Bergman's Projection on a Bounded Domain

In this paper exact asymptotic formulae are found for singularvalues of the Cauchy operator and the logarithmic potentialtype operator (on a bounded domain), as well as their productswith Bergman's projection. It is shown that these spectral characteristicsdetect geometric properties of a domain (area and the lengthof the boundary). The hypothesis "can we hear the shape of adrum", from a paper by J.M. Anderson, D. Khavinson, and V. Lomonosov[‘Spectral properties of some integral operators arisingin potential theory’, Quart. J. Math. Oxford (2) 43 (1992)387-407], is correct in the above sense. 1991 Mathematics SubjectClassification: 47B10.     

Far downstream analysis for the Blasius boundary-layer stability problem

In this paper, we examine the large Reynolds number (Re) asymptoticstructure of the wave number in the Orr–Sommerfeld regionfor the Blasius boundary layer on a semi-infinite flat plategiven by Goldstein (1983, J. Fluid Mech., 127, 59–81).We show that the inclusion of the term which contains the leading-ordernon-parallel effects, at O(Re^{– 1/2}), leads to a non-uniformexpansion. By considering the far downstream form of each termin the asymptotic expansion, we derive a length scale at whichthe non-uniformity appears, and compare this position with theposition seen in plots of the wave number.     

Electrochemical investigation of magnetite-carbon nanocomposite in situ grown on nickel foam as a high-performance binderless pseudocapacitor

Journal of Solid State Electrochemistry - Magnetite-carbon nanocomposite was grown in situ on nickel foam by a novel auto-combustion method, and it was investigated for application as a...