Structural transitions in polyribocytidylic acid induced by changes in pH and temperature: vibrational circular dichroism study in solution and film states

Changes in vibrational absorption and vibrational circular dichroism (VCD) spectra of polyribocytidylic acid (polyC) in buffered D(2)O solution as a function of pH and temperature are reported. Analysis of these spectral data led us to establish the absorption band at approximately 1693 cm(-1) and associated negative VCD couplet as diagnostic markers of the double-helical form of polyC. An alternate interpretation suggesting quadruplex formation for polyC is also discussed. In addition to the solution state spectral data, pH-dependent absorption and VCD spectra for polyC films derived from dilute H(2)O solutions are also presented. The pH-dependent changes in the absorption and VCD spectra of polyC films are found to be similar to those observed for polyC in solution.     

Compact Composition Operators and Deddens Algebras

We consider the Deddens algebras associated to compact composition operators on the Hardy space \(H^2\) on the unit disk. When the compact composition operator corresponds to a function \(\varphi \) that satisfies \(\varphi (0)=0\) and \(\varphi '(0)\ne 0\), we show that the lattice of invariant subspaces of this algebra is \(\{0\}\cup \{z^n H^2: n=0,1,2,\ldots \}\). As a consequence, for this class of operators the associated Deddens algebra is weakly dense in the algebra of lower triangular matrices.     

Design of self-cleaning TiO2 coating on clay roofing tiles

The phenomenon of heterogeneous photocatalysis takes place in the degradation process of many organic contaminants on solid surfaces. Photocatalysis is based on the excitation of the semiconductor by irradiation with supraband gap photons and the migration of electron-hole pairs to the surface of the photocatalysts, leading to the reaction of the holes with adsorbed H₂O and OH^? to form hydroxyl radicals. Due to the stability and photosensitivity of TiO₂ semiconductors, this system is well studied and is of great interest from an ecological and industrial point of view for use in the field of building materials. Clay roofing tiles, due to their long-term exploitation, are subject to physical, chemical and biological degradation that leads to deterioration. Ceramic systems have a high percentage of total porosity and considering their non-tolerance of organic coating, the use of surface active materials (SAM) that induce porosity in TiO₂ coatings is of vital significance. Photocatalytic coatings applied on clay roofing tiles under industrial conditions were designed by varying the quantity of TiO₂ (mass/cm²) on the tile surface (thin and thick TiO₂ layer). The positive changes in specific surface area and mesopore structure of the designed coatings were made by the addition of PEG 600 as a surface active material. It was shown that a thin photocatalytic layer (0.399 mg suspension/cm² tile surface), applied onto ceramic tiles under industrial conditions, had better photocatalytic activity in methylene blue decomposition, hydrophilicity and antimicrobial activity than a thick photocatalytic coating (0.885 mg suspension/cm²).     

Comparison of Inductively Coupled Plasma with Classical Analytical Techniques in the Analysis of Southern Oregon Lithia Water: Inclusion of a Local Resource in the Undergraduate Chemistry Curriculum

Abstract

Lithia water, a community resource of local historical significance, is described as a central theme in the undergraduate analytical chemistry sequence. A statistical comparison of the classical determination of major cations (Na⁺, K⁺, Ca²⁺, Mg²⁺) and anions (HCO₃ ^?, Cl^?) reinforces statistical and charge‐balance concepts covered in analytical chemistry. Subsequent determination of these major cations by inductively coupled plasma (ICP) enables students to statistically evaluate the presence of bias between instrumental and classical methods. The effect of easily ionized elements on ICP calibration sensitivity and linearity via the use of cesium as an ionization suppressor is reported.     

The quadruplex-duplex structural transition of polyriboguanylic acid

The vibrational infrared (IR) absorption and vibrational circular dichroism (VCD) spectral changes of polyriboguanylic acid (polyG) as a function of time, temperature and pH have been investigated to establish how changes in spectral features relate to the structural modifications of polyG. From the progression of IR and VCD spectral features with respect to time, it is observed that stabilization of the quadruplex structure at pH 6.4 (near-neutral environment) takes place within 5 days. This stabilization process is most clearly evidenced by a downshift of the carbonyl absorption band and the corresponding positive VCD couplet, from 1689 to approximately 1682 cm(-1) in time. Time-induced spectral modifications also indicated that, in an acidic environment (pH 3.1) and within a 5 day waiting period, polyG develops a duplex structure. An additional positive VCD couplet associated with an absorption band at 1589 cm(-1) is identified as a marker of the polyG duplex structure. From the progression of spectral features with respect to temperature at pH 6.4, it is found that heating induces structural changes that favor the formation of a duplex structure. This duplex structure, at pH 6.4, would not form at room temperature simply by the passage of time. When polyG is in an acidic environment (pH 3.1), heating accelerates the conversion to the duplex structure that could also be obtained with passage of time at that pH. On the basis of the comparison of experimental and quantum theoretical VCD spectra for polyG, the key spectral signature for the quadruplex form is considered to be a single positive VCD couplet, while the spectral signature for a duplex form is considered to contain an additional positive VCD couplet at a lower frequency.