Redox-induced conformational alteration of n,n-diarylamides

We constructed a novel molecular conformational alteration system with an N-aryl-N-phenylacetamide structure, in which the N-aryl group consists of a hydroquinone-p-quinone system as a redox-dependent aromatic trigger. The amide conformation depended on the oxidation state of the aryl group, and the two states (compounds 2 and 3) were reversibly converted to each other by redox reactions. Such compounds would be applied as useful structural units for external stimulus-responsive control on the shape and function of large molecules or supramolecules.     

Ultrasound-induced emission enhancement based on structure-dependent homo- and heterochiral aggregations of chiral binuclear platinum complexes

Instant and precise control of phosphorescent emission can be performed by ultrasound-induced gelation of organic liquids with chiral, clothespin-shaped trans-bis(salicylaldiminato)Pt(II) complexes, anti-1. Nonemissive solutions of racemic, short-linked anti-1a (n = 5) and optically pure, long-linked anti-1c (n = 7) in organic liquids are transformed immediately into stable phosphorescent gels upon brief irradiation of low-power ultrasound. Emission from the gels can be controlled by sonication time, linker length, and optical activity of the complexes. Several experimental results indicated that structure-dependent homo- and heterochiral aggregations and ultrasound-control of the aggregate morphology are key factors for emission enhancement.     

Spectrophotometric determination of cobalt(II) and cyanocobalamin with vanillilfluorone and its applications

Spectrophotometric determination of cobalt(II) was accomplished with vanillilfluorone (VF) in the presence of dimethylbenzyltetradecylammonium chloride (Zephiramine, Zep). In the determination of cobalt(II), Beer's law was obeyed in the range of 24-470 ng/ml, with an effective molar absorption coefficient (at 575 nm) and relative standard deviation of 1.35×10(5) l mol(-1) cm(-1) and 0.66% (n=5), respectively. The composition ratio of the colored complex was determined by the mole ratio and continuous variation methods, and it was found to be Co(II) : VF : Zep=1 : 2 : 4. Analysis of cyanocobalamin by the same procedure showed that cyanocobalamin could be determined in the concentration range of 0.5-0.11 μg/ml using the proposed method.     

My Father,My Grandfather

Note from the Editor: It is with great pleasure and enthusiasm that I introduce this essay which accompanies the publication of the fourth segment of the Tetsuo Nozoe Autograph Books. In the conceptualization stages of this project—which shall appear in 15 consecutive issues of The Chemical Record as well as have a significant internet presence—I proposed to my colleagues Eva Wille and Brian Johnson that each segment be accompanied with a specially invited essay or perspective. This proposal was immediately and enthusiastically accepted. To both celebrate the life and warmth of Tetsuo Nozoe, I can hardly imagine a more appropriate essay than one written by two of his grandchildren and one of his own children! I thank the Masamune Family for their touching contribution to this project. The Nozoe Autograph Books and all the accompanying essays, including this essay, are open access for at least a three‐year period at: http://www.tcr.wiley‐vch.de/nozoe . Jeffrey I. Seeman Guest Editor, University of Richmond Richmond, Virginia 23173, USA     

1H NMR and Calorimetric Studies of the Inclusion of Trimethylammonium Cations into Water Soluble Calixresorcinarenes

Abstract

The complexation of tetramethylammonium (TEMA), benzyltrimethylammonium (BTMA), p-nitrobenzyltrimethylammonium (BTMAN) and N, N, N-trimethylanilinium (TMA) by the tetrasulphonate derivative of the resorcinol cyclic tetramer (1), was studied in aqueous solution by ¹H NMR and calorimetry. Host 1 specifically recognizes the—N⁺ (CH₃)₃ group of TEMA, BTMA and BTMAN, whereas it binds TMA unselectively; TMA is included both via the charged group and the aromatic moiety. The binding constants of all four guests with 1, as determined by both ¹H NMR and calorimetric titrations, show that all inclusion processes are almost equally stabilised.

ΔHΔ and ΔSΔ values, determined by direct calorimetry, reveal specific interactions that are not expressed in the ΔGΔ terms and indicate that we are dealing with “non-classical hydrophobic effects”. The effects of the structural, conformational and electronic properties of the guests on the forces driving the inclusion processes are discussed.     

Evaluation of diffusional anisotropy and microscopic structure in skeletal muscles using magnetic resonance

The pulsed-gradient spin-echo (PGSE) nuclear magnetic resonance (NMR) method is used for detecting the diffusion of water molecules in biological tissues. Because tissues generally have diffusional anisotropy, their diffusion properties are denoted by a tensor. In this study, we evaluated the diffusional anisotropy and microscopic structure in atrophied skeletal muscles using the PGSE NMR method. The left sciatic nerve was severed in twelve 9-week-old rats. Neurotomy caused neurogenic muscular atrophy at the left gastrocnemius. At 2, 4 and 8 weeks after neurotomy, magnetic resonance signals were selectively acquired from a 2 x 2 x 2 mm(3) voxel, which was located on the left gastrocnemius. The diffusion tensor, the mean diffusivity (MD) and the fractional anisotropy (FA) were calculated from the signals. A theoretical model of the diffusion in muscles was derived from Tanner's equation. The muscle fiber diameter was estimated by fitting the model to the measured signals. The measurements were also performed for normal rats as controls. No significant difference was found in the MD and the estimated intracellular diffusion coefficient between the control group and the denervated group. The denervated group had significantly higher FA compared with the control group (P<.05). The estimated muscle fiber diameter of the denervated group was significantly smaller than the estimated value of the control group (P<.05). These differences were found at 8 weeks after neurotomy. The proposed method is effective for evaluating changes in the microscopic structure of skeletal muscles.     

Four different types of hydrogen bonds observed in 1,2-bis(N-benzenesulfonylamino)benzenes due to conformational properties of the sulfonamide moiety

The crystal structures of 1,2-bis(N-benzenesulfonylamino)benzenes with secondary and/or tertiary sulfonamide groups were determined by X-ray crystallographic analysis. Every Ar-sulfonamide group existed in synclinal conformation in the crystals even though it was secondary or tertiary. Each compound showed different types of hydrogen bonds in the crystal structure. 1,2-Bis(N-benzenesulfonylamino)benzene (1) formed two double hydrogen bonds connected to the next molecules, 1-(N-benzenesulfonylamino)-2-(N-benzenesulfonyl-N-methylamino)benzene (2) contained double hydrogen bond involved by both the sulfonamide moieties, 1,2-bis(N-4-toluenesulfonylamino)benzene (3) had both intra- and intermolecular hydrogen bonds, and 1-(N-methyl-N-4-toluenesulfonylamino)-2-(N-4-toluenesulfonylamino)benzene (4) had one double hydrogen bond involved by only one sulfonamide moiety. Sulfonamides 1 and 3 formed infinite arrays of the molecules, and sulfonamides 2 and 4 formed racemic dimer of their conformational enantiomers via the hydrogen bonds.     

Biosensing using lipid bilayers suspended on porous silicon

We demonstrate for the first time the formation of a fluid lipid bilayer membrane on mesoporous silicon substrates for bioapplications. Using fluorescence recovery after photobleaching, the diffusion coefficients for the bilayers supported on oxidized, amino-, and biotin-functionalized mesoporous silicon were determined. The biodetection of a single human umbilical vein endothelial cell was accomplished using confocal microscopy and exploiting Foerster resonance energy transfer effects after the incorporation of RGD covalently linked lipid soluble dyes, with fluorescence donor and acceptor components, within the fluid membrane. A signal response of greater than 100% was achieved via the clustering of RGD peptides binding with areas of high integrin density on the surface of a single cell. These results are a testament to the usefulness of such functional molecular assemblies, based on mobile receptors, mimicking the cell membrane in the development of a new generation of biosensors.     

Spontaneous resolution of aromatic sulfonamides: effective screening method and discrimination of absolute structure

An effective screening method combining parallel synthesis and solid-state CD measurements was established to identify achiral aromatic sulfonamides that show spontaneous resolution with rapidity. We found that 4 of the 12 achiral sulfonamides crystallized as chiral crystals through this method. The chirality of each sulfonamide was discriminated by solid-state CD spectra and Flack parameter in an X-ray analysis. Correspondence between the observed Cotton effect and the absolute configuration could be confirmed by time-dependent DFT calculations. [structure: see text]     

Structural and optical properties of Zn(Mg,Cd)O alloy films grown by remote-plasma-enhanced MOCVD

We report the structural and optical properties of wurtzite-structure Zn(Mg,Cd)O ternary alloys. Wurtzite (0 0 0 1) Zn_1−xCd_xO and Mg_yZn_1−yO films were grown on (11–20) sapphire substrates using remote-plasma-enhanced metalorganic chemical vapor deposition. The large bowing parameters of Zn_1−xCd_xO and Mg_yZn_1−yO ternary alloys are 3.0 and 3.5, respectively, which reflects the large difference of each binary’s electronegativity. We have analyzed the broadening of photoluminescence (PL) in Zn(Mg,Cd)O alloys on alloy content by taking into account the statistical alloy fluctuation and the localization of the exciton, and have clarified that the localization of the exciton strongly affects to PL full-width at half-maximum (FWHM) in Zn(Mg,Cd)O alloys. The alloy broadenings in steady-state PL of Zn(Mg,Cd)O alloys are in good agreement with the calculated tendency by the theoretical model based on the statistical alloy fluctuation, while PL FWHM of Zn_1−xCd_xO is three times larger than the calculated results. Moreover, as another way to confirm alloy broadening, we also have done time-resolved PL measurements and derived the localized depth of the exciton in ZnO-based system, indicating a good agreement with the tendency of PL FWHM broadening.