Gas ebullition from petroleum hydrocarbons in aquatic sediments: A review.

Gas ebullition in sediment results from biogenic gas production by mixtures of bacteria and archaea. It often occurs in organic-rich sediments that have been impacted by petroleum hydrocarbon (PHC) and other anthropogenic pollution. Ebullition occurs under a relatively narrow set of biological, chemical, and sediment geomechanical conditions. This process occurs in three phases: I) biogenic production of primarily methane and dissolved phase transport of the gases in the pore water to a bubble nucleation site, II) bubble growth and sediment fracture, and III) bubble rise to the surface. The rate of biogenic gas production in phase I and the resistance of the sediment to gas fracture in phase II play the most significant roles in ebullition kinetics. What is less understood is the role that substrate structure plays in the rate of methanogenesis that drives gas ebullition. It is well established that methanogens have a very restricted set of compounds that can serve as substrates, so any complex organic molecule must first be broken down to fermentable compounds. Given that most ebullition-active sediments are completely anaerobic, the well-known difficulty in degrading PHCs under anaerobic conditions suggests potential limitations on PHC-derived gas ebullition. To date, there are no studies that conclusively demonstrate that weathered PHCs can alone drive gas ebullition. This review consists of an overview of the factors affecting gas ebullition and the biochemistry of anaerobic PHC biodegradation and methanogenesis in sediment systems. We next compile results from the scholarly literature on PHCs serving as a source of methanogenesis. We combine these results to assess the potential for PHC-driven gas ebullition using energetics, kinetics, and sediment geomechanics analyses. The results suggest that short chain 

Aryl trihydroxyborate salts: thermally unstable species with unusual gelation abilities.

A series of aryl trihydroxyborate salts were synthesized and found to form gels in benzene. The compounds were thermally unstable and readily underwent protodeboronation in solution and the solid state. Gelation could be induced without decomposition via sonication. Subsequent characterization studies revealed an unusual dependence of gel properties on alkyl chain length.

Sulfonatocalix[8]arene as a potential reaction cavity: photo- and electro-active dicationic guests arrest conformational equilibrium.

Smaller members of water-soluble sulfonated calixarenes have been extensively explored in the context of host-guest complexation, supramolecular chemistry, and potential sensors. However, larger members especially eight-membered calixarene (CA[8]) has received much less attention because of its floppy nature and tendency to exist as a mixture of conformational isomers. Our continued interest in identifying molecules with an internal cavity as reaction vessels has led us to examine the host-guest complexation of CA[8] with photoactive bispyridyl ethylenes. We find that 4,4'-bispyridyl ethylene and 3,3'-bispyridyl ethylene upon complexation to CA[8] arrest the conformational equilibrium and force the latter to adopt a single conformation in solution. During complexation, bispyridyl ethylenes are protonated by the sulfonic acid groups of CA[8]. The host-guest complex is stabilized via an electrostatic interaction between the cationic bispyridyl ethylenes and anionic sulfonated calix[8]arene, and we propose the complex to have an inverted capsular structure. This model is also consistent with the electrochemical behavior of 4,4'-dimethylviologen included within CA[8]. Rigidification of bispyridyl ethylenes by the host has a consequence on the excited-state chemistry of the former. Generally, prevalent geometric isomerization of bispyridyl ethylenes are prevented by CA[8] upon complexation.

Crystal engineering principles applied to solution photochemistry: controlling the photodimerization of stilbazolium salts within gamma-cyclodextrin and cucurbit[8]uril in water.

Borrowing concepts from crystal engineering techniques we have been able to steer the photodimerization of stilbazolium salts included in gamma-cyclodextrin towards a desired dimer.

Templating photodimerization of stilbazoles with water-soluble calixarenes.

Water soluble six and eight membered calixarenes template the dimerization of trans-stilbazoles. In the absence of calixarenes at the concentrations employed stilbazoles mainly isomerize to the corresponding cis isomers. Calixarenes help to localize the olefins and orient them in a specific geometry to yield anti-head-tail dimers. Electrostatic interaction between the sulfonate anion and the pyridinium ion of the olefin and hydrophobic interaction between the olefin and the host cavity are believed to be responsible for the observed selectivity. (1)H NMR spectra provide evidence for complexation but do not suggest the exact structure of the host-guest complex.

Template directed photodimerization of trans-1,2-bis(n-pyridyl)ethylenes and stilbazoles in water.

Template induced photodimerization of trans-1,2-bis(n-pyridyl)ethylene dihydrochlorides and trans-n-stilbazole hydrochlorides within cucurbit[8]uril in aqueous media leads to high yields of the syn dimer.

A latent photoreaction predominates within water-soluble calixarenes: photochemistry of benzoin alkyl ethers.

Benzoin alkyl ethers encapsulated in a cisoid conformation within water-soluble p-sulfonatocalix[8]arenes preferentially yield the Norrish Type II reaction product deoxybenzoin.