Spectrofluorimetric Determination of Second Critical Micellar Concentration of SDS and SDS/Brij 30 Systems

Potentially useful stead-state fluorimetric technique was used to determine the critical micellar concentrations (CMC(1) and CMC(2)) for two micellar media, one formed by SDS and the other by SDS/Brij 30. A comparative study based on conductimetric and surfacial tension measurements suggests that the CMC(1) estimated by the fluorimetric method is lower than the value estimated by these other techniques. Equivalent values were observed for SDS micelles without Brij 30 neutral co-surfactant. The use of acridine orange as fluorescent probe permitted to determine both CMC(1) and CMC(2). Based on it an explanation on aspects of micelle formation mechanism is presented, particularly based on a spherical and a rod like structures.     

Energy conversion process from the photoexcited electronic states studied by the temperature lens and acoustic peak delay methods in solution

Ultrafast temperature rise after the deactivation of the electronically excited state of 2-hydroxybenzophenone in various solvents is investigated by two photothermal techniques; temperature lens and acoustic peak delay methods, and by the population grating technique. The results from these methods show that the thermalization process takes place by two phases; fast (<1 ps) and rather slow (30 ps) processes. From the solvent dependence of the thermalization rate, we suggest that these processes are related with the intermolecular interaction and the solvation structure around the photoexcited molecules.     

Four copper(II) complexes with potentially tetradentate tripodal ligands

The four title Cu^II compounds are chloro­[(2‐furyl­methyl)­bis(2‐pyridyl­methyl)­amine‐N,N′,N′′]copper(II) perchlorate, [CuCl(C₁₇H₁₇N₃O)]ClO₄, (I), chloro{2‐[bis(2‐pyridyl­methyl)­amino]­ethano­lato‐N,N′,N′′,O}­copper(II) hemi­[tetra­chloro­copper(II)], [CuCl(C₁₄H₁₇N₃O)][CuCl₄]_1/2, (II), chloro­[(2‐morpholino­ethyl)­bis(2‐pyridyl­methyl)­amine‐N,N′,N′′,N′′′]copper(II) perchlorate, [CuCl(C₁₈H₂₄N₄O)]ClO₄, (III), and chloro­[(2‐piperidinyl­ethyl)­bis(2‐pyridyl­methyl)­amine‐N,N′,N′′,N′′′]­copper(II) hexa­fluoro­phosphate, [CuCl(C₁₉H₂₆N₄)]­PF₆, (IV). They have tripodal potentially tetradentate ligands. In (I), the O atom of the furan moiety weakly coordinates to the Cu atom at a distance of 2.750 (3) Å.     

Step bunching behaviour on the {0 0 0 1} surface of hexagonal SiC

Surface topography of the {0 0 0 1} facet plane of as-grown 6H- and 4H-SiC crystals was studied ex situ by Nomarski optical microscopy (NOM) and atomic force microscopy (AFM). The surface polarity and the polytype of grown crystals largely affect the growth surface morphology of SiC{0 0 0 1} via differences in several thermodynamic and kinetic parameters. NOM observations revealed giant steps of a few micrometers in height on the {0 0 0 1} growth facet, and it was found that a morphological transition of the growth facet occurred when the growth conditions were changed. AFM imaging of the stepped structure of SiC{0 0 0 1} detected steps of height equal to the unit c-lattice parameter (c=1.512 nm for 6H-SiC and 1.005 nm for 4H-SiC). They are fairly straight and very regularly arranged, giving rise to equidistant step trains. Upon nitrogen doping, these regular step trains on the 6H-SiC(0 0 0  )C and 4H-SiC(0 0 0  )C surfaces became unstable: the equidistant step trains were transformed into meandering macrosteps of height greater than 10 nm. In this paper, we discuss the mechanism of macrostep formation (step bunching) on the SiC{0 0 0 1} surfaces through the consideration of the interplay between step energetics (repulsive step interaction) and kinetics (asymmetric step kinetics) on the growing crystal surface and elucidate how they affect the growth surface morphology of the SiC{0 0 0 1} facet.     

An organic white light-emitting fluorophore

The synthesis of new benzo[a]- and [b]xanthene dye frameworks is described. A unique benzo[a]xanthene, seminaphtho[a]fluorone (SNAFR-1), is studied in a variety of media. The optimization of solution parameters and excitation wavelengths allows SNAFR-1 to display red, green, and blue emission bands of approximately equal intensities and also to produce white light. Ratiometric red (anion) and green (neutral) emissions are observed upon varying solution pH. A pH-independent violet-blue emission band is due to the addition of nucleophiles to the benzylic carbon of SNAFR-1.     

Generation of carbamoyl- and thiocarbamoyllithium synthons having a hydrogen(s) or an aryl group on the nitrogen and their trapping with carbonyl electrophiles

Dimetalated amides 1 (Y = O) were generated as the synthons of carbamoyllithiums 2 (Y = O) by the reaction of isocyanates with iBu2AlTenBu and a subsequent tellurium-lithium exchange reaction. A series of amide derivatives 3 (Y = O) were obtained by the trapping of dianion 1 with electrophiles. This transformation can be successfully applied to the generation and trapping of thiocarbamoyllithium synthons 1 (Y = S) as well as to the nucleophilic introduction of the parent carbamoyl moiety H2NC(O).     

Stereochemical and regiochemical trends in the selective detection of saccharides

Several discreet sugar-boronate complexes exist in solution. This is due to the complex equilibria between isomeric species of even the simplest monosaccharides. In the current investigation, we determine the regio- and stereochemical features of the various equilibrating sugar isomers that induce signal transduction in boronic acid chemosensors such as 1 as well as 2 and 3. We present a unique example of a chemosensor (1) that is selective for ribose, adenosine, nucleotides, nucleosides, and congeners. As a result of this study, we are able to predict and achieve selective fluorescence and colorimetric responses to specific disaccharides as a consequence of their terminal sugar residue linkage patterns and configurations. We also find that the combined use of chemosensors exhibiting complementary reactivities may be used cooperatively to obtain enhanced selectivity for ribose and rare saccharides.     

Crystal structures and magnetic properties of complexes of M(II)Cl2 (M = Cu, Ni, and Co) coordinated with 4-(N-tert-butyloxyamino)-2-(methoxymethylenyl)pyridine: 2D magnetic anisotropy of the aminoxyl-Co(II) complex in the crystalline state

Three metal complexes, [M(II)Cl2(4NOPy-OMe)2] (M = Cu (1), Ni (2), and Co (3)), were prepared by mixing the corresponding metal chloride and 4-(N-tert-butyloxyamino)-2-(methoxymethylenyl)pyridine, 4NOPy-OMe, in 1:2 ratio. Complex 1 has two structures (complexes A and B) with similar coordination geometries, compressed octahedrons. In the crystal structure, complexes A and B locate alternately in short distances (C(radical)...C(beta) = 3.17 and 3.23 A) to form a 1-D chain structure. Complexes 2 and 3 are isomorphous and have a slightly distorted octahedral structure. In the crystal structure, both complexes have intermolecular short contacts (C(radical)...C(alpha) = 3.46 and 3.52 A for 2 and 3, respectively) to form the 2-D structures. The temperature dependence of the chi(mol)T values for the three complexes indicated that the magnetic interactions between the radicals and the metal ions within the complexes were ferromagnetic. By fitting a modified Fisher 1-D model to the data of the chi(mol)T vs T plot for 1, we estimated the intra- and intermolecular (intrachain) exchange coupling constants to be J1/kB = 60.2 and J2/kB = -7.02 K, respectively. On the other hand, complexes 2 and 3 showed steep increases of the chi(mol)T value below ca. 3 K, indicating that the long-range magnetic ordering is operating. The 1/chi(mol) vs T plot for 2 was analyzed by a Curie-Weiss model to give theta = 6.25 K and C = 2.02 cm3 K mol(-1) with g(Ni) = 2.25. Complex 3 was investigated in more detail using an orientated sample. Magnetic behavior strongly depends on the direction of the applied field, in which the c axis perpendicular to the ab plane is an easy axis for magnetization. Direct current (dc) and alternating current (ac) magnetic susceptibility measurements revealed that complex 3 had a magnetic phase transition of T(c) = 2.14 K and exhibited a glasslike magnetic behavior below T(c).     

Spectroscopic and excited-state properties of tri-9-anthrylborane II: Electroabsorption and electrofluorescence spectra

Electroabsorption and electrofluorescence spectroscopies were conducted for tri-9-anthrylborane (TAB) doped in poly(methyl methacrylate) films (1.0 mol %) to reveal the spectroscopic and excited-state properties of the compound. TAB showed three distinct absorption bands: bands I [(19 - 25) x 10(3) cm(-1)], II [(25-31) x 10(3) cm(-1)], and III (>31 x 10(3) cm(-1)). The electroabsorption spectrum demonstrated that the electronic transitions in bands I and III accompanied electric dipole moment changes (Deltamu), while the change in the molecular polarizability contributed mainly to electroabsorption band II. Because of the similarities of the electroabsorption spectrum of band II with that of anthracene itself, band II was assigned to the electronic transition to the locally excited (LE) state of the anthryl group. On the other hand, bands I and III were best described by the electronic transitions to the excited charge-transfer (CT) states. The study demonstrated furthermore that the Deltamu value of TAB accompanied by the lowest-energy electronic transition was as large as 7.8 D, which agreed very well with that determined by the solvent dependences of the absorption and fluorescence maximum energies of TAB (approximately 8.0 D, ref 1): Deltamu = 7.8-8.0 D. The results proved explicitly that the excited state of TAB was localized primarily on the p orbital of the boron atom. Despite the dipole moment change (Deltamu = 7.8-8.0 D) for the lowest-energy electronic transition (band I), the electrofluorescence of TAB accompanied the change in the molecular polarizability. The spectroscopic and excited-state properties of TAB including the curious behavior of the electrofluorescence spectrum as mentioned above were discussed on the basis of theoretical considerations.