Bruce L. Jensen

Dual WO3 based sensors to selectively detect DMMP in the presence of alcohols

A size selective approach to improving selectivity in semiconducting metal oxides (SMO) sensors was obtained by tailoring the architecture of WO(3) powders. The key for achieving high selectivity is based on using a dual sensor configuration where the response on a porous WO(3) powder sensor was compared to the response on a nonporous WO(3) powder sensor. Detection selectivity between methanol and dimethyl methylphosphonate (DMMP) is obtained because the access of a gas molecule in the interior pore structure of WO(3) is size dependent leading to a size dependant magnitude change in the conductivity of SMO sensor.

Infrared study of UV-irradiated tungsten trioxide powders containing adsorbed dimethyl methyl phosphonate and trimethyl phosphate

The photodecomposition of dimethyl methylphosphonate (DMMP) and trimethyl phosphate (TMP) adsorbed on monoclinic WO3 powders when irradiated by ultraviolet light (UV) in air, oxygen, and under evacuation was investigated using infrared spectroscopy (IR). The IR spectra show that DMMP decomposes into methyl phosphonate upon exposure to 254 nm UV for 2 h at room temperature in air. The same decomposition of DMMP occurs only at temperatures above 300°C without UV illumination. TMP differs from DMMP in that the photodecomposition product is not the same as the decomposition product obtained by heating above 300°C. Thermal decomposition leads to formation of a phosphate on the surface, whereas photodecomposition leads to the same adsorbed methyl phosphonate as found for the thermal or photodecomposition of DMMP. Since TMP does not contain a P-CH3 bond, the formation of a methyl phosphonate on the surface after UV illumination involves a mechanism where CH3 groups migrate from the methoxy group to the phosphorous central atom. No decomposition is observed at room temperature when DMMP or TMP adsorbed on WO3 is irradiated under vacuum or in nitrogen atmosphere. Therefore, the photodecomposition of either DMMP or TMP adsorbed on WO3 at room temperature does not involve a reaction with the lattice oxygen but rather a reaction with the oxygen radicals produced by the decomposition of ozone.

A concise synthesis of 1-substituted-2-tetralones by selective diol dehydration leading to ketone transposition

Dehydration of 1-substituted-1,2-tetralindiols with zinc iodide aAorded the corresponding 2-tetralones in excellent yields. This procedure was found to be superior to the more conventional BF3-catalyzed rearrangement of 1-substituted-1,2-epoxytetralins. # 2000 Elsevier Science Ltd. All rights reserved.

Plant Hormones Isolated from “Katahdin” Potato Plant Tissues and the Influence of Photoperiod and Temperature on Their Levels in Relation to Tuber Induction

Qualitative and quantitative analyses were carried out on vegetative tissues of potato (Solanum tuberosum cv. “Katahdin”) in search of natural products thought to play a role in tuber induction. Tissues were obtained from plants initially grown in a growth chamber under noninducing conditions (30°C day and 28°C night with an 18-h photoperiod), and then half of the plants were moved to inducing chambers (28°C day and 13°C night with a 10-h photoperiod) for 10 days prior to tissue harvest. Plants from each chamber were then harvested at 2-day intervals for 10 days, separated into above- and belowground portions, and the lyophilized tissues were extracted and subjected to rigorous purification and separation using high-performance liquid chromatography. This was followed by identification and quantification using combined gas chromatography-mass spectrometry. Compounds isolated and identified included gibberellic acid; cytokinins cis-zeatin riboside, trans-zeatin, trans-zeatin riboside, and isopentenyladenine; and jasmonates jasmonic acid, tuberonic acid and its methyl ester, methyl 7-isocucurbate, and 9,10-dihydromethyljasmonate. Methyl 7-isocucurbate and 9,10-dihydromethyljasmonate were detected for the first time in potato tissue as endogenous compounds. Cytokinin and jasmonate levels generally increased under inducing conditions, whereas gibberellic acid levels declined progressively during the 10-day sampling period. Only gibberellic acid, jasmonic acid, and cis-zeatin riboside levels were significantly influenced by induction.

Chelation controlled allylation of aldehydes with a chiral allylsilylene derived from (−)-10-phenylpinanediol

Abstract The chiral allylsilylene prepared from (−)-10-phenylpinanediol reacts with chiral α-alkoxy aldehydes in the presence of stannic chloride to afford homoallylic alcohols with diastereofacial selectivity ratios as high as 100:0. The results are consistent with attack of the allylsilylene on the less hindered face of the chelated intermediate. Our preliminary studies on several silylenes prepared from bicyclo[3.1.1] systems revealed that substituent effects on the chiral auxiliary and the silicon atom play an important role in the selectivity of these unique compounds.

Kinetic studies and improved reaction conditions for the halogen shift rearrangments of aryldihalopropanols

Abstract Solvolytic data were obtained from the acid catalyzed trifluoroacetolysis of 1-(o-chlorophenyl)-2,2-dichloro-1-propyl trifluoroacetate (1a-TFA) and the analogous 2,2-dibromo trifluoroacetate 1b-TFA which implicate a halonium ion intermediate in the rearrangement to an α-haloketone. Employing the conditions used to achieve kinetic control, substantial increases in yield were realized for those compounds which reacted too rapidly in and were unstable to concentrated sulfuric acid (i.e. 1b and 1c).