Templated synthesis of glycoluril hexamer and monofunctionalized cucurbit[6]uril derivatives

We report that the p-xylylenediammonium ion (11) acts as a template in the cucurbit[n]uril forming reaction that biases the reaction toward the production of methylene bridged glycoluril hexamer (6C) and bis-nor-seco-CB[10]. Hexamer 6C is readily available on the gram scale by a one step synthetic procedure that avoids chromatography. Hexamer 6C undergoes macrocylization with (substituted) phthalaldehydes 12, 14, 15, and 18-in 9 M H(2)SO(4) or concd HCl at room temperature to deliver monofunctionalized CB[6] derivatives 13, 16, 17, and 19-that are poised for further functionalization reactions. The kinetics of the macrocyclization reaction between hexamer and formaldehyde or phthalaldehyde depends on the presence and identity of ammonium ions as templates. p-Xylylenediammonium ion (11) which barely fits inside CB[6] sized cavities acts as a negative template which slows down transformation of 6C and paraformaldehyde into CB[6]. In contrast, 11 and hexanediammonium ion (20) act as a positive template that promotes the macrocyclization reaction between 6C and 12 to deliver (±)-21 as a key intermediate along the mechanistic pathway to CB[6] derivatives. Naphthalene-CB[6] derivative 19 which contains both fluorophore and ureidyl C═O metal-ion (e.g., Eu(3+)) binding sites forms the basis for a fluorescence turn-on assay for suitable ammonium ions (e.g., hexanediammonium ion and histamine).     

Electric field gradient in Mg and Zn detected by β-emitters,8Li and12x0392;x0392;x0392;

The quadrupole coupling constants of⁸Li and¹²B in hcp Mg and Zn are determined by use of a newly developed nuclear quadrupole resonance technique (NNQR) as ¦eqQ(⁸Li in Mg)/h¦=3.0±0.3 kHz, ¦eqQ(⁸Li in Zn)/h¦=33.5±2 kHz, and ¦eqQ(¹²B in Mg)/h¦=47.0±0.1 kHz. Correspondingly, the electric field gradients at room temperature are deduced: ¦q(⁸Li in Mg)¦=(3.81±0.39)×10¹⁸, ¦q(⁸Li in Zn)¦=(4.25±0.27)×10¹⁹, and ¦q(¹²B in Mg)¦=(1.47±0.03)×10²⁰, all in V/m². The experiments are compared with the results of first-principles super-cell band structure calculations which can treat local lattice relaxations around the impurity nuclei. The calculations show that the most favorable location of these light interstitials in hcp Mg is not the octahedral-like sites which have the biggest interstitial volume, but the basal trigonal sites with a local lattice expansion of as big as 30%. Calculated electric field gradients at the impurity nuclei reproduce the experimental values fairly well.     

Starting energy and current for a large diameter finite lengthbackward wave oscillator operated at the fundamental mode

We study the starting conditions for a large diameter (diameter/wavelength=4.8) finite length backward wave oscillator designed for 24-GHz operation at the fundamental TM₀₁ mode. This geometry is very promising for high power handling capability. We analyze two separate threshold conditions. First, finite length effects give rise to a threshold in electron beam energy below which oscillations cannot be sustained at any beam current. The second is the more familiar current threshold known as a start current. It is also found that the growth rate for the fundamental mode can be much larger than those of other higher order modes thus leading to coherent operation of large diameter sources free from mode competition     

Determination of chromium, copper and lead in river water by graphite-furnace atomic absorption spectrometry after coprecipitation with terbium hydroxide.

Coprecipitation with terbium hydroxide quantitatively recovered trace amounts of chromium(III), copper(II) and lead(II) at pH 8.4 - 10.8, 8.0 - 11.5 and 8.7 - 11.5, respectively. The precipitate was dissolved in 0.85 mol dm(-3) nitric acid, and the analytes were determined by graphite-furnace atomic absorption spectrometry (GF-AAS). The presence of terbium (up to 7 g dm(-3)) did not interfere with the determination. The detection limits were 0.3 microg dm(-3) for chromium, 0.4 microg dm(-3) for copper and 0.5 microg dm(-3) for lead, when the analytes in 200 cm3 of the sample solution were concentrated into 10 cm3. The ions added to river or seawater were quantitatively recovered. Chromium and copper in a contaminated river water were successfully determined.     

Formation of Superhydrophobic Alumina Coating Films with High Transparency on Polymer Substrates by the Sol-Gel Method

Transparent, superhydrophobic coating films have been prepared on polymer substrates at low temperatures through the sol-gel method. Al₂O₃ gel films were prepared on poly(ethylene terephthalate) substrates from Al(O-sec-C₄H₉)₃ chemically modified with ethyl acetoacetate. A small roughness of about 20–50 nm was found to form on the surface of the Al₂O₃ gel films dried at room temperature and then immersed in hot water at 60°C. The electron diffraction measurements have shown that this roughened surface consists of pseudoboehmite nanocrystals. The coating of hydrolyzed fluoroalkyltrimethoxysilane on the Al₂O₃ gel films with the small roughness produced transparent, superhydrophobic films with contact angle for water larger than 150°.     

Weak Pareto optimality of multiobjective problems in a locally convex linear topological space

Several corrections to Ref. 1 are pointed out.     

Identification of gas emanated from human skin: methane, ethylene, and ethane.

We investigated whether methane, ethylene and ethane gas can be detected in gas emanating from human skin, which is called skin gas. Skin gas was collected with a homemade stainless-steel trap system, which was cooled with liquid nitrogen, and analyzed with a gas chromatograph fitted with a flame ionization detector (FID). Skin-gas samples were obtained by covering a hand for 30 min with a polyfluorovinyl bag in which pure helium gas was introduced. The bag, the trap system and GC were set up online to avoid any contamination by air. Methane, ethylene and ethane in skin gas were successfully collected at an average amount emanated for 30 min (from ten subjects) of 150 +/- 63, 20 +/- 11 and 17 +/- 8 [mean +/- SD] pg/cm2, respectively.     

Time-resolved ESR study of the lowest excited triplet states of para-quinones in glassy matrices at 77 k

The lowest excited nπ* triplet of 9.10-anthraquinone, 1.4-naphthoquinone and 1,4-benzoquinone were studied in glassy matrices at 77 K using a time-resolved ESR method. The D value of the triplet state of 9,10-anthraquinone varied from ?0.351 cm^?1 in a polar solvent to ?0.318 cm^?1 in a non-polar solvent. Both 1,4-naphthoquinone and 1,4-benzoquinone in polar solvents showed triplet state spectra with a D value of ?0.330 cm^?1. A computer simulation revealed the existence of widely distributed zero-field splitting parameters in the glassy condition. These data are compared with an analysis of CIDEP results of para-quinones.