The Use of Derivative Thermogravimetry to Estimate Degree of Thermal Degradation

It is difficult to estimate the degree of thermal degradation which has taken place in complex parts composed of cellulosics and polymeric insulation unless complete failure has occurred. There is a definite need for a parameter which can quickly and easily measure the relative degree of thermal attack on organic insulation subjected to various known environmental and processing conditions. This paper reports preliminary work using derivative thermogravimetry to perform this function. Derivative thermogravimetric analysis (TGA) was used to produce a value, TGA Index, related to the peak height of the major TGA derivative signal. This TGA Index was found to correlate with the copper number of insulating paper measured after thermal degradation. The application of TGA Index to evaluation of polymer degradation after thermal shock, water absorption, and accelerated UV attack is also discussed. Finally, preliminary studies on the use of derivative TGA to evaluate coatings exposed to various outdoor environments around the country are reported.     

Structural Characterization of the Condensation Polymer of Dipyridine Manganese II Dichloride with 1,3-Di-4-piperidy I propane

The synthesis of polymers derived from the condensation of dipyridine manganese II dichloride with 1,3-di-4-piperidylpro-pane is described. Structural analysis of the polyamines is detailed utilizing results based on infrared, thermal, elemental and solution analyses.     

Type I Photosensitization of 2′‐deoxyadenosine 5′‐monophosphate (5′‐dAMP) by Biopterin and its Photoproduct Formylpterin

Biopterin (Bip) and its photoproducts 6‐formylpterin (Fop) and 6‐carboxypterin (Cap) accumulate in the skin of patients suffering from vitiligo, a chronic depigmentation disorder where the protection against UV radiation fails because of the lack of melanin. These compounds absorb in the UV‐A inducing a potential photosensitizing action that can cause damage to DNA and other biomolecules. In this work, we have investigated the capability of these pterin derivatives (Pt) to act as photosensitizers under UV‐A irradiation for the degradation of 2′‐deoxyadenosine 5′‐monophosphate (5′‐dAMP) in aqueous solutions, as model DNA target. Steady‐state and time‐resolved experiments were performed and the effect of pH was evaluated. The results showed that photosensitized degradation of 5′‐dAMP was only observed under acidic conditions, and a mechanistic analysis revealed the participation of the triplet excited state of the pterin derivatives (³Pt*) by electron transfer yielding the corresponding pair of radical ions (Pt^?? and 5′‐dAMP^?+), with successive photosensitizer recovery by electron transfer from Pt^?? to O₂. Finally, 5′‐dAMP^?+ participates in subsequent reactions to yield degradation products.     

Dual Electroactivity in a Covalent Organic Network with Mechanically Interlocked Pillar[5]arenes

The synthesis and characterization of a polyrotaxanated covalent organic network (CON) based on the association between the viologen and pillar[5]arene (P[5]OH) units are reported. The mechanical bond allows for the irreversible insertion of n-type redox centers (P[5]OH macrocycles) within a pristine structure based on p-type viologen redox centers. Both redox units are active on a narrow potential range and, in water, the presence of P[5]OH greatly increases the electroactivity of the material.     

A simple polymer electrolyte membrane system for enrichment of low-level tritium (3H) in environmental water samples

Tritium (³H) is an essential tracer of the Earth's water cycle; yet widespread adoption of tritium in hydrologic studies remains a challenge because of analytical barriers to quantification and detection of ³H by electrolytic pre-concentration. Here, we propose a simple tritium electrolytic enrichment system based on the use of solid polymer electrolyte membranes (PEMs) that can be used to enrich ³H in 250–3000?mL environmental water samples to a 10-mL final volume. The IAEA PEM-³H system reported here can produce high enrichment factors (>70-fold) and, importantly, removes some of the deterrents to conventional ³H enrichments methods, including the use of toxic electrolysis and neutralization chemicals, spike standards, a complex electrolysis apparatus that requires extensive cooling and temperature controls, and improves precision by eliminating the need for tracking recovery gravimetrics. Preliminary results with varying operating conditions show ³H enrichments to 70-fold and higher are feasible, spanning a wide range of tritium activities from 5 to 150 TU with a precision of ～4.5?%. Further work is needed to quantify inter-sample memory and to establish lower ³H detection limits. The IAEA PEM-³H system is open source, with 3-D CAD and design files made freely available for adoption and improvement by others.     

Stereoselective Ketone Rearrangements with Hypervalent Iodine Reagents

The first stereoselective version of an iodine(III)‐mediated rearrangement of arylketones in the presence of orthoesters is described. The reaction products, α‐arylated esters, are very useful intermediates in the synthesis of bioactive compounds such as ibuprofen. With chiral lactic acid‐based iodine(III) reagents product selectivities of up to 73 % ee have been achieved.