Energy Development in Colorado's Pawnee National Grasslands: Mapping and Measuring the Disturbance Footprint of Renewables and Non-Renewables.

This paper examines the pattern and extent of energy development in steppe landscapes of northeast Colorado, United States. We compare the landscape disturbance created by oil and gas production to that of wind energy inside the Pawnee National Grasslands eastern side. This high-steppe landscape consists of a mosaic of federal, state, and private lands where dominant economic activities include ranching, agriculture, tourism, oil and gas extraction, and wind energy generation. Utilizing field surveys, remote sensing data and geographic information systems techniques, we quantify and map the footprint of energy development at the landscape level. Findings suggest that while oil and gas and wind energy development have resulted in a relatively small amount of habitat loss within the study area, the footprint stretches across the entire zone, fragmenting this mostly grassland habitat. Futhermore, a third feature of this landscape, the non-energy transportation network, was also found to have a significant impact. Combined, these three features fragment the entire Pawnee National Grasslands eastern side, leaving very few large intact core, or roadless areas. The primary objective of this ongoing work is to create a series of quantifiable and replicable surface disturbance indicators linked to energy production in semi-arid grassland environments. Based on these, and future results, we aim to work with industry and regulators to shape energy policy as it relates to environmental performance, with the aim of reducing the footprint and thus increasing the sustainability of these extractive activities.

Arylazopyrazoles: azoheteroarene photoswitches offering quantitative isomerization and long thermal half-lives.

Arylazopyrazoles, a novel class of five-membered azo photoswitches, offer quantitative photoswitching and high thermal stability of the Z isomer (half-lives of 10 and ∼1000 days). The conformation of the Z isomers of these compounds, and also the arylazopyrroles, is highly dependent on the substitution pattern on the heteroarene, allowing a twisted or planar geometry, which in turn has a significant impact on the electronic spectral properties of the compounds.

A computational study of remote C-H activation by amine radical cations: implications for the photochemical reduction of carbon dioxide.

A computational study, using density functional theory calibrated against higher-level methods, has been undertaken to evaluate tertiary amines whose radical cations might lose hydrogen atoms from positions other than the alpha carbons. The purpose was to find photochemically activated reducing agents for carbon dioxide that could be regenerated in a separate photochemical reaction. The calculations have revealed two reactions that might be suitable for this purpose. In one, the nitrogen of the radical cation makes a bond to a remote carbon with simultaneous displacement of a hydrogen atom. In the other, a remote hydrogen atom is transferred to the nitrogen, thereby creating a distonic radical cation that can lose a hydrogen atom beta to the radical site. The latter reaction is found to be particularly favorable since it apparently involves a surface crossing that allows the amine radical cation and CO2 radical anion to transform smoothly to a ground-state formate ion and an alkene. A number of structural motifs are investigated for the amines. The lower ionization potential of aromatic amines, compared to their aliphatic analogues, is desirable in that it could permit the use of longer wavelength light to drive the reaction. However, a thermochemical cycle shows that the reduction in ionization potential must be matched by an increase in proton affinity of the amine if the intramolecular hydrogen transfer is to be exothermic. Most aromatic amines do not satisfy this criterion and, hence, would have to rely on the displacement reaction for hydrogen-atom release if they were to be used as renewable reagents for CO2 reduction. Examples of specific aromatic and aliphatic tertiary amines that should be suitable for the purpose are presented, and their relative merits and weaknesses are discussed.

Photoswitchable basicity through the use of azoheteroarenes.

Azoheteroarene photoswitches offer functional advantages over their more conventional azobenzene counterparts by virtue of their heteroaromatic ring(s). Here we report that azobis(2-imidazole) functions as a photoswitchable base due to the additional proton stabilisation that is possible in the protonated Z isomer, facilitated by the basic imidazole nitrogens. This thermodynamic difference in stability corresponds to a 1.3 unit difference in pK(a) values between the E and Z isomers. This pK(a) difference can be used to reversibly control solution pH.

Dual wavelength asymmetric photochemical synthesis with circularly polarized light.

Asymmetric photochemical synthesis using circularly polarized (CP) light is theoretically attractive as a means of absolute asymmetric synthesis and postulated as an explanation for homochirality on Earth. Using an asymmetric photochemical synthesis of a dihydrohelicene as an example, we demonstrate the principle that two wavelengths of CP light can be used to control separate reactions. In doing so, a photostationary state (PSS) is set up in such a way that the enantiomeric induction intrinsic to each step can combine additively, significantly increasing the asymmetric induction possible in these reactions. Moreover, we show that the effects of this dual wavelength approach can be accurately determined by kinetic modelling of the PSS. Finally, by coupling a PSS to a thermal reaction to trap the photoproduct, we demonstrate that higher enantioselectivity can be achieved than that obtainable with single wavelength irradiation, without compromising the yield of the final product.

A renewable amine for photochemical reduction of CO(2).

Photochemical reduction of CO2 (to produce formic acid) can be seen both as a method to produce a transportable hydrogen-based fuel and also to reduce levels of CO2 in the atmosphere. However, an often overlooked necessity for photochemical CO2 reduction is the need for a sacrificial electron donor, usually a tertiary amine. Here, we describe a new strategy for coupling the photochemical reduction of CO2 to photochemical water splitting, and illustrate this with a prototype example. Instead of seeking to eliminate the use of an external reducing agent altogether, our alternative strategy makes the reducing agent recyclable. This has two potential advantages over the direct coupling of CO2 reduction and water oxidation. First, it allows the two redox reactions to be carried out with existing chemistry, and second, it permits these reactions to be conducted under mutually incompatible conditions.

Origin of diastereocontrol in the oxy-Michael reactions of delta-lactol anions: a computational and experimental study.

The diastereoselectivity in the alkylation and Michael addition of "naked" 6-substituted delta-lactolates has been studied by density functional (B3LYP) calculations with ab initio (MP2) energy refinements. The resulting proposed model for the origins of stereocontrol in this reaction has been tested by experiment. The reactions lead to a high cis diastereoselectivity across the THP ring due to the preference for both the alkoxide and the 6-substituent to sit equatorial in the alkylation transition structure. In the oxy-Michael addition of these lactolates to beta-substituted nitroolefins, we propose that the high diastereoselectivity beta- to the nitro group is a result of a combination of steric, stereoelectronic and solvation factors.

Hypervalent iodine-mediated aziridination of alkenes: mechanistic insights and requirements for catalysis.

By detailed study of the possible side reactions in the previously reported aziridination of alkenes with N-aminoheterocycles mediated by hypervalent iodine reagents, the requirements to make this reaction catalytic in iodoarene have been determined. The reaction requires an oxidant that will oxidise iodoarenes but that does not oxidise alkenes, but it is possible that no such oxidant actually exists! A method in which the hypervalent iodine reagent can be recycled without the need for reisolation is possible. Further study into the mechanism of this reaction gives tentative evidence that the reaction proceeds through formation of an aminoiodane that reacts directly with the alkene, contrary to previous literature reports in which an acetoxyamine intermediate is suggested. The temperature effect of this reaction is remarkable.