THE PRESENCE OF PHOTOREACTIVE β-CARBOLINE FLUOROPHORES IN WEATHERED WOOL KERATIN

Abstract Solvent-cleaned Merino wool, which was enzymatically digested with protease K, displayed a fluorescence maximum at 500 nm when excited at 430 nm. The yield of this emission was approximately 15 times greater for a fiber tips digest than for a digest of the mid-length region of the same fibers.
Separation of the components in the wool tip digest by silica gel thin-layer chromatography revealed the presence of several fluorescent species. The chromatographic mobility of these species was similar to the behavior observed in a preparation of authentic 1-methyltetrahydro-P-carboline, 1,3-dicarboxylic acid.
Mass spectroscopy of the fluorescent compounds in the wool tip digest displayed molecular ions, [M + H]⁺ with m/z = 273.0890 and 257.0560, and molecular weights that define the formulae C₁₄H₁₂N₂O₄ and C₁₁H₈O₄N₂, respectively, which correspond to β-carboline 1,3-dicarboxylic acids. Mass spectral evidence also indicates the presence of two other β-carbolines.     

The determination of small amounts of long-chain tertiary alkylamines and quarternary ammonium salts

Bromocresol green has been investigated as an alternative to ammonium erdmannate for the absorptiometric determination of small amounts of long-chain alkylamines and quaternary ammonium salts in aqueous solution in a solvent extraction procedure. The molecular absorption coefficient of the reagent at 615 nm is about 3 times that of the erdmannate ion at 353 nm; visual methods of comparison are simplified by the blue colour of the bromocresol green anion The sensitivity of both the bromocresol green and the erdmannate method may be increased by stripping the coloured reagents into a small volume of aqueous solution. Both methods are free of interference from iron, but the present procedure has the disadvantage of a blank which depends both on the pH and on the concentration of excess reagent.     

The arrangement of first- and second-shell water molecules in trivalent aluminum complexes: results from density functional theory and structural crystallography

The structural and energetic features of a variety of gas-phase aluminum ion hydrates containing up to 18 water molecules have been studied computationally using density functional theory. Comparisons are made with experimental data from neutron diffraction studies of aluminum-containing crystal structures listed in the Cambridge Structural Database. Computational studies indicate that the hexahydrated structure Al[H(2)O](6)(3+) (with symmetry T(h)()), in which all six water molecules are located in the innermost coordination shell, is lower in energy than that of Al[H(2)O](5)(3+).[H(2)O], where only five water molecules are in the inner shell and one water molecule is in the second shell. The analogous complex with four water molecules in the inner shell and two in the outer shell undergoes spontaneous proton transfer during the optimization to give [Al[H(2)O](2)[OH](2)](+).[H(3)O(+)](2), which is lower in energy than Al[H(2)O](6)(3+); this finding of H(3)O(+) is consistent with the acidity of concentrated Al(3+) solutions. Since, however, Al[H(2)O](6)(3+) is detected in solutions of Al(3+), additional water molecules are presumed to stabilize the hexa-aquo Al(3+) cation. Three models of a trivalent aluminum ion complex surrounded by a total of 18 water molecules arranged in a first shell containing 6 water molecules and a second shell of 12 water molecules are discussed. We find that a model with S(6) symmetry for which the Al[H(2)O](6)(3+) unit remains essentially octahedral and participates in an integrated hydrogen bonded network with the 12 outer-shell water molecules is lowest in energy. Interactions between the 12 second-shell water molecules and the trivalent aluminum ion in Al[H(2)O](6)(3+) do not appear to be sufficiently strong to orient the dipole moments of these second-shell water molecules toward the Al(3+) ion.     

The synthesis of poly(acrylic acid hydrazide) and poly(methylacrylic acid hydrazide) and their reaction products with ribonucleoside dialdehydes

Atactic and syndiotactic poly(acrylic acid hydrazide) and atactic, syndiotactic and isotactic poly(methylacrylic acid hydrazide) have been reacted with the di-aldehydes derived from adenosine, guanosine, inosine, cytidine and uridine to give polymers each containing a single type of base residue. Not all of the hydrazide residues of the polymeric hydrazides reacted; guanosine dialdehyde gave the most reaction and inosine dialdehyde the least. Isotactic poly(methylacrylic acid hydrazide) was much less reactive than the other polymeric hydrazides. The adenine-containing and the cytosine-containing polymers with atactic backbones had a low solubility in water whereas those with syndiotactic backbones had a relatively high solubility. For a given polymeric hydrazide backbone the adenine-containing polymers were always the least soluble in water. Most of the ribonucleoside dialdehyde-containing polymers, with the exception of those containing uridine dialdehyde, had only a low solubility in salt solution (0.3M sodium chloride, 0.03M trisodium citrate). No evidence could be obtained for any interaction of these polymers with polynucleotides.     

Intramolecular Nonbonded Interactions Between Oxygen and Group VIA Elements: An Ab Initio Molecular Orbital and Density Functional Theory Investigation of the Structures of HX—CH2—COOH (X=S,Se, and Te)

Ab initio molecular orbital and density functional methods have been used to study the potential energy surfaces of the substituted acetic acids HX—CH₂—COOH, where X is one of the Group VIA Chalcophiles S, Se, or Te. The various conformers adopted by these compounds provide information regarding the energetic importance of nonbonded and hydrogen bonding interactions involving oxygen atoms with different hybridizations. Density functional and ab initio molecular orbital methods yield similar structural and energetic trends for these compounds. Calculations show that the structure of the lowest-energy conformer of each of these acids has the X—C—C—O backbone substantially twisted from planarity, similar to that previously observed for the corresponding aldehydes, HX—CH₂—CHO. In the twisted acid structures the shortest distance is within about 0.1 Å of the sum of the X and O van der Waals radii, which reduces overcrowding of the lone pairs of electrons on these atoms. In conformers where the heavy atom backbone is planar, one of the distances is significantly shorter than the sum of the van der Waals radii, and the total molecular energy of these conformers is higher than that of the twisted forms. The variation of X—H vibrational frequencies among conformers reflects the extent of X—H hydrogen bonding, and indicates that formation of this hydrogen bond is not the dominant factor in determining the lowest-energy conformation. When X is oxygen (HO—CH₂—COOH), the lowest-energy conformer is also nonplanar, whereas for the corresponding aldehyde, HO—CH₂—CHO, the lowest-energy conformer is a planar structure with C_S symmetry. The conformational preferences of these simple species provide reference points for inter- and intramolecular interactions in more complex systems of biological interest.     

X-Ray Structure and Proton NMR Study of a Hexacoordinated Lithium Complex

The structure of the lithium complex with1,3,5-tris[oxymethylene(N,N-dicyclohexyl)carboxyamido]cyclohexanehas been determined by the X-ray method.The compound is triclinic, space group P¯1,a = 15.623(3), b = 19.279(4),c = 19.295(4)Å = 102.32(3), = 92.45(3), = 105.67(3)0, V = 5436(2)Å3, Z = 4. Itscomposition is represented by the formulaC48H82N3O6LiI 0.5H2O. The lithium cationis encapsulated in a polar pseudo-cavity of six oxygen atoms of the ligandmolecule and displays a distorted trigonal prism coordination. The conformationof the ligand in the solid state complex has been compared with the conformationof the complex in solution determined by 1H-NMR measurements.Supplementary data relevant to this publication have been deposited with the British Library, No. SUP 82224 (21 pages).     

High‐efficiency polymer solar cells based on phenylenevinylene copolymer with BF2‐azopyrrole complex and CN‐PC70BM with solvent additive

Power conversion efficiency (PCE) of phenylenevinylene‐based copolymer with BF₂ azopyrrole complex (PB)/modified PC₇₀BM, that is, CN‐PC₇₀BM bulk heterojunction solar cells improves from 2.16 to 4.90% using a processing additive and drying condition. The results demonstrate that a processing additive and drying condition provides an effective means to control both the surface roughness and finer interpenetrating networks to enhance the exciton dissociation into free charge carriers, charge transportation, and collection. Taking into the account of simple device fabrication process without thermal annealing, the PCE of the polymer solar cell can further improved by chloronapthalene (CN) additive under the fast drying condition. The average carrier lifetimes extracted from the impedance spectra and found to correlate with measured PCEs. At short circuit conditions and illumination, the average charge carrier lifetime was found vary from 16.8 to 32 μs with power conversion efficiencies ranging from 3.0 to 4.9%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

MIR imaging bundles of ordered silver halide polycrystalline fibres for thermal transmission and imaging

This study aims to experimentally examine the energy-saving potential by using R-134a filled separated two-phase thermosiphon loop (STPTL) for data center applications. A parametric study had been made to compare the energy consumption of two data center racks. Two fin-and-tube heat exchangers were attached to one of the racks to form two individual thermosiphon loops. The experiments were carried out subject to different operating conditions, including three ambient temperatures (20 °C, 23 °C, and 27 °C) and filling ratios ranging from 30 to 90% in association with heating loads ranging between 1.5 kW and 6 kW. Parametric influences regarding concentrated heat loading or uniform heat loading are studied. It was found that an appreciable energy-savings can be obtained at high filling ratios and a maximum of 49% energy-saving with the assistance of thermosiphon is observed. Accordingly, the rising of system pressure will result in noticeable savings. Relative to the uniform heat loading of the data rack, the thermosiphon shows even more energy-saving potential in concentrated heat loading. This phenomenon is more pronounced at a lower ambient temperature like 20 °C. On the other hand, there is no appreciable energy-saving for the thermosiphon between concentrated and uniform heating loads when the ambient temperature is high (27 °C). Furthermore, the influence of airflow rate was also investigated under various ambient temperatures with a 90% filling ratio and a heating load of 6 kW. The results revealed that the lower airflow rate in the thermosiphon yields comparatively better energy-saving than the higher flow rate. The study on the influence of using two STPTLs indicated that 15–23% energy-saving can be achieved at a 90% filling ratio and 6 kW heating load for all the studied ambient conditions if compared with testing each loop separately. Lower thermal resistance is seen at the higher filling ratios, ambient temperatures, and heating loads.

     

An extension of moments calculations for optical absorption bands

In this paper the developments of Henry, Schnatterly and Slichter are extended by using a more general formulation of the principle of spectroscopic stability (for a site of symmetry O_h). The linear effects for any type of stress are obtained next. The expressions indicate how one can test the theory experimentally in a critical manner. This has not been done. The theory shows that one cannot expect to get more information on KCl from stress experiments than is now available. Finally, it is indicated how one may define the irreducible stresses and strains in an unambiguous manner by using the differential strain-energy function.     

Optical properties of mesoporous II-VI semiconductor compound films

Direct liquid crystal templating from non-ionic polyoxyethylene surfactants has been utilised to produce well-defined birefringent films of nanostructured cadmium telluride films which displayed good optical properties as evidenced by UV/VIS reflectance spectroscopy.