Extending the semi-empirical PM6 method for carbon oxyacid pKa prediction to sulfonic acids: Application towards congener-specific estimates for the environmentally and toxicologically relevant C1 through C8 perfluoroalkyl derivatives

A positive bias in the semi-empirical PM6 method for estimating pKa values of sulfonic acids was corrected by a correlation developed between non-adjusted PM6 pKa values and the corresponding experimentally obtained/estimated acidity constants for a range of representative alkyl, aryl, and halogen substituted sulfonic acids. Application of this correction to PM6 values allows for extension of this computational method to a new acid functional group

Examining the PM6 semiempirical method for pKa prediction across a wide range of oxyacids

The pK~a~ estimation ability of the semiempirical PM6 method was evaluated across a broad range of oxyacids and compared to results obtained using the SPARC software program. Compound classes under consideration included acetic acids, alicyclic and aromatic heterocyclic acids, benzoic acids, boronic acids, hydroxamic acids, oximes, peroxides, peroxyacids, phenols, α-saturated acids, α-saturated alcohols, sulfinic acids, α-unsaturated acids, and α-unsaturated alcohols. PM6 accurately predicts the acidity of acetic and benzoic acids and their derivatives, but is less reliable for alicyclic and aromatic heterocyclic acids and phenols. α-Saturated acids are reliably modeled by PM6 except for polyacid derivatives with α-alcohol moieties. α-Saturated alcohols only appear to yield reliable PM6 results where an α-hydroxy or α-alkoxy moiety is absent. Carboxylic acids with simple α-alkene unsaturation are well approximated by PM6 except where alkyne α-unsaturation or α-carboxylation are also present. The PM6 and SPARC methods exhibit approximately equal pKa prediction performance for the acetic, alicyclic, and benzoic acids. SPARC outperforms PM6 on the peroxides, peroxyacids, phenols, and α-saturated acids and α-saturated alcohols. pKa values for boron, nitrogen, and sulfur oxyacids do not appear to be reliably estimated by either the PM6 or SPARC methods. The findings will help guide the potential appropriateness of results from the PM6 pK~a~ estimation method for waste treatment and environmental fate investigations

Predicting the Congener-Specific Environmental Behaviour of Perfluorinated Acid Contaminants Using Semi-Empirical Computational Methods

Perfluorinated acids (PFAs) are contaminants detected worldwide in a range of abiotic and biotic environmental matrices. The two major classes of PFAs include the perfluorinated carboxylic acids (PFCAs) and perfluorinated sulfonic acids (PFSAs), both of which are considered persistent and potentially bioaccumulative. Current research and regulatory efforts are focussed on the straight-chain members of each PFA class and homologue group, primarily because these congeners are the major components of technical mixtures and are also available as pure standards. However, the numerous potential branched congeners in each PFA class represent a poorly understood family of environmental contaminants whose environmental and toxicological properties may be more important than the more prevalent straight-chain members. To help broaden the current understanding of PFA environmental fate and toxicology, semi-empirical computational methods were used predict fundamental physico-chemical properties of all potential C4 to C8 PCFA and PFSA congeners. Established quantitative structure-activity models for other multi-class emerging and legacy contaminants were applied to estimate key parameters related to the toxicology, environmental partitioning, and abiotic and biotic degradation mechanisms for each PFA class. The findings provide guidance for developing new analytical methods for separating and identifying PFAs in environmental and technical mixtures, prioritizing efforts on synthesizing authentic standards, and focussing toxicological studies on the congeners most likely to be of concern

Rolling-joint design optimization for tendon driven snake-like surgical robots

The use of snake-like robots for surgery is a popular choice for intra-luminal procedures. In practice, the requirements for strength, flexibility and accuracy are difficult to be satisfied simultaneously. This paper presents a computational approach for optimizing the design of a snake-like robot using serial rolling-joints and tendons as the base architecture. The method optimizes the design in terms of joint angle range and tendon placement to prevent the tendons and joints from colliding during bending motion. The resulting optimized joints were manufactured using 3D printing. The robot was characterized in terms of workspace, dexterity, precision and manipulation forces. The results show a repeatability as low as 0.9mm and manipulation forces of up to 5.6N

Suspended particles are hotspots of microbial remineralization in the ocean's twilight zone

The sinking of photosynthetically produced organic carbon from the ocean surface to its interior is a significant term in the global carbon cycle. Most sinking organic carbon is, however, remineralized in the mesopelagic zone (∼100 m–1000 m), thereby exerting control over ocean-atmosphere carbon dioxide (CO2) partitioning and hence global climate. Sinking particles are considered hotspots of microbial respiration in the dark ocean. However, our observations in the contrasting Scotia Sea and the Benguela Current show that >90% of microbial remineralisation is associated with suspended, rather than sinking, organic matter, resulting in rapid turnover of the suspended carbon pool and demonstrating its central role in mesopelagic carbon cycling. A non-steady-state model indicates that temporally variable particle fluxes, particle injection pumps and local chemoautotrophy are necessary to help balance the observed mesopelagic respiration. Temperature and oxygen exert control over microbial respiration, particularly for the suspended fraction, further demonstrating the susceptibility of microbial remineralisation to the ongoing decline in oxygen at mid-ocean depths. These observations suggest a partial decoupling of carbon cycling between non-sinking and fast-sinking organic matter, challenging our understanding of how oceanic biological processes regulate climate

Trifluoroacetic Acid::Toxicity, Sources, Sinks and Future Prospects

Trifluoroacetic acid (TFA) is a known persistent pollutant in the environment. Although several direct anthropogenic sources exist, production from the atmospheric degradation of fluorocarbons such as some hydrofluorocarbons (HFCs) has been a known source for some time. The current transition from HFCs to HFOs (hydrofluoroolefins) is beneficial from a global warming viewpoint, because HFOs are much shorter-lived and pose a much smaller threat to warming, but the fraction of HFO conversion to TFA is higher than for the corresponding HFCs and the region over which the TFA is produced is close to the source. Therefore, it is timely to review the role of TFA in the Earth’s environment. This review considers its toxicity, sources and removal processes, measurements in a variety of environments and future prospects. New global model integrations quantify the impacts on TFA levels of uncertainties in the Henry’s Law constant for TFA and the range of gas-phase kinetic parameters determined for the reaction of OH radicals with a representative HFO (HFO-1234yf). Model runs suggest that TFA surface concentrations vary by up to 10% based on Henry’s Law data, but could be up to 25% smaller than previously modelled values depending on the kinetic analysis adopted. Therefore, future estimates of TFA surface concentrations based on HFO removal re-quire updating and the kinetic analysis of TFA production warrants further investigation. The toxicity of TFA appears to be low but further studies of a much wider range of animal and plant types are required

Investigating the atmospheric sources and sinks of Perfluorooctanoic acid using a global chemistry transport model

Perfluorooctanoic acid, PFOA, is one of the many concerning pollutants in our atmosphere; it is highly resistant to environmental degradation processes, which enables it to accumulate biologically. With direct routes of this chemical to the environment decreasing, as a consequence of the industrial phase out of PFOA, it has become more important to accurately model the effects of indirect production routes, such as environmental degradation of precursors; e.g., fluorotelomer alcohols (FTOHs). The study reported here investigates the chemistry, physical loss and transport of PFOA and its precursors, FTOHs, throughout the troposphere using a 3D global chemical transport model, STOCHEM-CRI. Moreover, this investigation includes an important loss process of PFOA in the atmosphere via the addition of the stabilised Criegee intermediates, hereby referred to as the “Criegee Field.” Whilst reaction with Criegee intermediates is a significant atmospheric loss process of PFOA, it does not result in its permanent removal from the atmosphere. The atmospheric fate of the resultant hydroperoxide product from the reaction of PFOA and Criegee intermediates resulted in a ≈0.04 Gg year−1 increase in the production flux of PFOA. Furthermore, the physical loss of the hydroperoxide product from the atmosphere (i.e., deposition), whilst decreasing the atmospheric concentration, is also likely to result in the reformation of PFOA in environmental aqueous phases, such as clouds, precipitation, oceans and lakes. As such, removal facilitated by the “Criegee Field” is likely to simply result in the acceleration of PFOA transfer to the surface (with an expected decrease in PFOA atmospheric lifetime of ≈10 h, on average from ca. 80 h without Criegee loss to 70 h with Criegee loss)