Modeling Small Structural and Environmental Differences in Solids with 15N NMR Chemical Shift Tensors

The ability to theoretically predict accurate NMR chemical shifts in solids is increasingly important due to the role such shifts play in selecting among proposed model structures. Herein, two theoretical methods are evaluated for their ability to assign ¹⁵N shifts from guanosine dihydrate to one of the two independent molecules present in the lattice. The NMR data consist of ¹⁵N shift tensors from 10 resonances. Analysis using periodic boundary or fragment methods consider a benchmark dataset to estimate errors and predict uncertainties of 5.6 and 6.2 ppm, respectively. Despite this high accuracy, only one of the five sites were confidently assigned to a specific molecule of the asymmetric unit. This limitation is not due to negligible differences in experimental data, as most sites exhibit differences of >6.0 ppm between pairs of resonances representing a given position. Instead, the theoretical methods are insufficiently accurate to make assignments at most positions.     

Development of One-Step Non-Solvent Extraction and Sensitive UHPLC-MS/MS Method for Assessment of N-(n-Butyl) Thiophosphoric Triamide (NBPT) and N-(n-Butyl) Phosphoric Triamide (NBPTo) in Milk

N-(n-butyl) thiophosphoric triamide (NBPT) is a urease inhibitor utilised in urea-based fertilizers. In Ireland, fertilizer treated with NBPT is applied to pasture to mitigate both ammonia and nitrous oxide emissions, but concerns arise as to the potential for residues in milk products. A quick ultrafiltration extraction and ultra-high performance liquid chromatography coupled with mass spectrometry triple quadrupole (UHPLC-MS/MS) quantitation method was developed and validated in this study. The method was applied in the analysis of samples collected from a field study investigating potential transfer of NBPT residues into milk. NBPT and NBPTo residues, were extracted from fortified milk samples and analysed on a UHPLC-MS/MS with recoveries ranging from 74 to 114%. Validation of the UHPLC-MS/MS method at low (0.0020 mg kg⁻¹) and high (0.0250 mg kg⁻¹) concentration levels in line with SANTE/12682/2019 showed overall trueness in the range of 99 to 104% and precision between 1 and 10%, RSD for both compounds. The limit of quantitation (LOQ) was 0.0020 mg kg⁻¹ and other tested parameters (linearity, sensitivity, specificity, matrix effect, robustness, etc.) satisfied acceptance criteria. Stability assessment using spiked samples revealed the compounds were stable in raw and pasteurised milk for 4 weeks at –80 °C storage temperature. Maintaining samples at pH 8.5–9.0 further improved stability. Analysis of 516 milk samples from the field study found that NBPT and NBPTo concentrations were below the LOQ of 0.0020 mg kg⁻¹, thus suggesting very low risk of residues occurring in the milk. The method developed is quick, robust, and sensitive. The method is deemed fit-for-purpose for the simultaneous determination of NBPT and NBPTo in milk.     

Thermomechanical enhancement of DPP-4T through purposeful π-conjugation disruption

The design of polymer-based organic semiconductors that offer mechanical deformability while maintaining efficient semiconducting characteristics remains a significant challenge. Recent synthetic efforts have incorporated small alkyl segments directly into otherwise π-conjugated polymer backbones to enhance processability, mechanical deformability, and other properties. The resulting polymers can be used as stand-alone materials or as matrix polymers in complementary semiconducting polymer blends offering reasonable charge-carrier transport properties, thermal healing, and deformability. Here, a family of diketopyrrolopyrrole-tetrathiophene variants is explored via large-scale atomistic molecular dynamics simulations to examine the effect of alkyl segments incorporated into the polymer backbone on the polymer structure, dynamics, and thermal properties. Longer alkyl segments lead to polymer chains that are more flexible, compact, and mobile, with lower glass transition temperatures for the condensed phase.     

Combining TOUGH2 and FLAC3D to Solve Problems in Underground Gas Storage

This paper describes modeling studies assessing the feasibility of increasing the maximum storage pressure in several underground natural gas storage reservoirs. This required an assessment of the potential for gas transport in the caprock and the geomechanical response to pressure change in the storage reservoir. To solve this problem in an efficient manner, two-phase flow (TOUGH2) and geomechanical (FLAC3D) models were combined in series. The TOUGH2 model was calibrated to fit pressure data collected on-site, from both the reservoir and caprock. The mechanical response of the caprock to increased storage pressure was modeled using FLAC3D, allowing assessment of the induced stresses in formations surrounding the reservoirs. We focused on two sites. In the first, field data were obtained from a deep borehole above the gas reservoir, which provided indirect observations of the geomechanical response of the caprock to pressure changes in the reservoir. In the second, open boreholes intersecting two thin caprock units immediately above the reservoir allowed gas flow to a shallower unit, significantly impacting the modeled fracture gradient.     

The stability of Tenax TA thermal desorption tubes in simulated field conditions on the HAPSITE® ER

Due to the growing need to monitor aircraft cabin, cockpit and breathing-line air quality, functional assessment of sampling equipment for the specialised field conditions of flight need to be established for both in-flight and ground safety. In this article, we assess the reliability of Tenax TA thermal desorption tubes to perform under various relevant field sampling conditions, such as storage temperature, loading temperature, vibrational velocity, gravitational force (G Force) and altitude pressure with semi-real-time gas chromatograph-mass spectrometer (GC-MS) analysis on the field portable HAPSITE^® ER (Hazardous Air Pollutants on Site Extended Range) instrument. First, we show that Tenax TA thermal desorption tubes can handle storage under extreme environmental conditions, 4–77°C, over numerous analytical test cycles. Next, we confirm that extreme loading temperature, both hot (77°C) and cold (4°C), does not affect the analytical reliability of Tenax TA thermal desorption tubes. Then, we illustrate that G Force may have a significant (p ≤ 0.0364) effect on Tenax TA performance while vibrational velocity (p ≤ 0.7265) and low ambient air pressure (p ≤ 0.1753), such as that found at high altitude, do not. Finally, several Tenax TA thermal desorption tubes were flight-tested, demonstrating that the durability of these tubes maybe insufficient for use on military cargo aircraft (p = 0.0107). The results presented here provide a rationale for additional testing of Tenax TA thermal desorption tubes for flight suitability.     

Ionic Conductivity of the NASICON-Related Thiophosphate Na1+xTi2−xGax(PS4)3

Inspired by the recent interest in fast ionic conducting solids for electrolytes, the ionic conductivity of a novel ionic conductor Na_1+xTi_2−xGa_x(PS₄)₃ has been investigated. Using X-ray diffraction and impedance spectroscopy the sodium ionic conductivity in this compound was demonstrated, in which bond valence sum analysis suggests a tunnel diffusion for Na⁺. Substitution with Ga³⁺ leads to an increasing Na⁺ content, an expansion of the lattice and an increasing conductivity with increasing x in Na_1+xTi_2−xGa_x(PS₄)₃. Given the relation to the NASICON family, upon replacement of the phosphate by a thiophosphate group, a rich structural chemistry can be expected in this class of materials. This work demonstrates the potential for making NaTi₂(PS₄)₃ an ideal system to study structure-property relationships in ionic conductors.     

CMM-RS potential for characterization of the properties of the halogen-bonded OC-Cl2 complex, and a comparison with hydrogen-bonded OC-HCl

Transitions associated with the vibrations ν?, ν? + ν(b)1, ν? + ν?1, and ν? + ν?1 - ν?1 of the complex OC···Cl? have been rovibrationally analyzed for several isotopologues involving isotopic substitutions in Cl?. Spectra were recorded using a recently constructed near-infrared (4.34 to 4.56 μm), quantum-cascade laser spectrometer with cw supersonic slit jet expansion. Spectral analysis allowed precise determination of the ν?1 intermolecular vibration of OC-3?Cl? to be 25.977637(80) cm?1. These results were incorporated with other previously determined data into a spectroscopic database for generation of a five-dimensional morphed potential energy surface. This compound-model morphed potential with radial shifting (CMM-RS) was then used to make more accurate predictions of properties of the OC-3?Cl? complex including D(e) = 544(5) cm?1, D? = 397(5) cm?1, ν? = 56.43(4) cm?1, and ν(b)1 = 85.43(4) cm?1. The CMM-RS potential determined for OC-Cl? was also used to compare quantitatively many of the inherent properties of this non-covalent halogen bonded complex with those of the closely related hydrogen-bonded complex OC-HCl, which has a similar dissociation energy D?. We found that in the ground state, the CO bending amplitude is larger in OC-Cl? than in OC-HCl.     

OH-initiated heterogeneous aging of highly oxidized organic aerosol

The oxidative evolution ("aging") of organic species in the atmosphere is thought to have a major influence on the composition and properties of organic particulate matter but remains poorly understood, particularly for the most oxidized fraction of the aerosol. Here we measure the kinetics and products of the heterogeneous oxidation of highly oxidized organic aerosol, with an aim of better constraining such atmospheric aging processes. Submicrometer particles composed of model oxidized organics-1,2,3,4-butanetetracarboxylic acid (C(8)H(10)O(8)), citric acid (C(6)H(8)O(7)), tartaric acid (C(4)H(6)O(6)), and Suwannee River fulvic acid-were oxidized by gas-phase OH in a flow reactor, and the masses and elemental composition of the particles were monitored as a function of OH exposure. In contrast to our previous studies of less-oxidized model systems (squalane, erythritol, and levoglucosan), particle mass did not decrease significantly with heterogeneous oxidation. Carbon content of the aerosol always decreased somewhat, but this mass loss was approximately balanced by an increase in oxygen content. The estimated reactive uptake coefficients of the reactions range from 0.37 to 0.51 and indicate that such transformations occur at rates corresponding to 1-2 weeks in the atmosphere, suggesting their importance in the atmospheric lifecycle of organic particulate matter.