Modification of a Common ß-diketiminate NacNac Framework via Sequential Lithiation and Small Molecule Insertion.

A widely utilised class of ligands in synthesis and catalysis, ß-diketiminate (BDI) or NacNac compounds were initially considered innocent in the sense that they remained intact in all their applications. That changed when the γ-C-H unit of their NCCCN backbone was found to engage in reactions with electrophiles. Here, we show that this special reactivity can be used advantageously to prepare tripodal modifications of the common NacNac ligand derived from 2,6-diisopropylphenyl-ß-methyldiketimine [NacNacH (Me, Dipp)]. Lithiation to give NacNacLi, followed by reactions with isocyanates, isothiocyanates and a carbodiimide, have afforded a series of tripodal NacNac variants having N,N,N,O; N,N,N,S; or N,N,N,N potential dentation sites, many of which have been crystallographically characterised. Distinct ligating modes of these new ligands have been elucidated through the crystal structures of their lithiated derivatives.

Molecular Formula Prediction for Chemical Filtering of 3D OrbiSIMS Datasets.

Modern mass spectrometry techniques produce a wealth of spectral data, and although this is an advantage in terms of the richness of the information available, the volume and complexity of data can prevent a thorough interpretation to reach useful conclusions. Application of molecular formula prediction (MFP) to produce annotated lists of ions that have been filtered by their elemental composition and considering structural double bond equivalence are widely used on high resolving power mass spectrometry datasets. However, this has not been applied to secondary ion mass spectrometry data. Here, we apply this data interpretation approach to 3D OrbiSIMS datasets, testing it for a series of increasingly complex samples. In an organic on inorganic sample, we successfully annotated the organic contaminant overlayer separately from the substrate. In a more challenging purely organic human serum sample we filtered out both proteins and lipids based on elemental compositions, 226 different lipids were identified and validated using existing databases, and we assigned amino acid sequences of abundant serum proteins including albumin, fibronectin, and transferrin. Finally, we tested the approach on depth profile data from layered carbonaceous engine deposits and annotated previously unidentified lubricating oil species. Application of an unsupervised machine learning method on filtered ions after performing MFP from this sample uniquely separated depth profiles of species, which were not observed when performing the method on the entire dataset. Overall, the chemical filtering approach using MFP has great potential in enabling full interpretation of complex 3D OrbiSIMS datasets from a plethora of material types.

Time resolved growth of (N)-polycyclic aromatic hydrocarbons in engine deposits uncovered with OrbiSIMS depth profiling.

Carbonaceous deposits are ubiquitous, being formed on surfaces in engines, fuel systems and on catalysts operating at high temperatures for hydrocarbon transformations. In internal combustion engines, their formation negatively affects worldwide vehicle emissions and fuel economy, leading to premature deaths and environmental damage. Deposit composition and formation pathways are poorly understood due to their insolubility and the intrinsic complexity of their layered carbonaceous matrix. Here, we apply the in situ high mass resolving power capabilities of 3D Orbitrap secondary ion mass spectrometry (3D OrbiSIMS) argon cluster depth profiling on 16 lab grown deposits and evidence common molecular distributions in deposit depth and in positions relative to the combustion chamber. We observe the products of the growth of both planar and curved polycyclic aromatic hydrocarbons to form small fullerenes over time in the engine and propose possible formation pathways which explain the molecular distributions observed. These include alkyl scission, cyclisation of aliphatic side chains and hydrogen abstraction C2H2 addition to form larger aromatic structures. We apply this pathway to previously unidentified nitrogen containing structures in deposits including quinolines and carbazoles. For the first time, 3D OrbiSIMS results were compared and validated with data from atmospheric pressure matrix assisted laser desorption ionization MS. The comprehensive characterization provided will help the development of a new generation of chemical additives to reduce deposits, and thus improve vehicle emissions and global air quality.

Expected and Unexpected Reactivities of Homoleptic LiNacNac and Heteroleptic NacNacMg(TMP) ß-Diketiminates toward Various Small Unsaturated Organic Molecules.

Homoleptic LiNacNac forms simple donor-acceptor complexes with N,N'-dicyclohexylcarbodiimide (CyN═C═NCy), triphenylphosphine oxide (Ph3P═O), and benzophenone (Ph2CO). These crystallographically characterized compounds could be regarded as model intermediates en route to reducing the N═C, P═O, and C═O bonds of unsaturated substrates. Heteroleptic NacNacMg(TMP) intriguingly functions as a TMP nucleophile both with t-BuNCO and t-BuNCS, producing a urea or thiourea derivative respectively attached to Mg, though the NacNac ligand in the former reaction also engages noninnocently with a second t-BuNCO molecule via insertion at the reactive NacNac backbone γ-carbon site.

Backbone Reactivity of Lithium ß-Diketiminate (NacNac) Complexes with CO2 , tBuNCO and iPrNCO.

Though alkali metal NacNac (ß-diketiminate) complexes have been utilised in synthesis as NacNac-transfer agents, studies of them in their own right with small molecules are exceptionally rare. Here, the lithium compound of the common 2,6-diisopropylphenyl-ß-methyldiketiminate [NacNac(Dipp, Me)] ligand is investigated with carbon dioxide and isocyanates. In all four cases reaction occurs at the backbone γ-C atom of the NacNac ligand, which redistributes electronically into a diimine. Insertion of CO2 gives an eight-atom carboxylate (Li2 O4 C2 ) ring at the γ-C site in a dimer. Insertion of tBuNCO gives a secondary amide at the γ-C site in a monomer with TMEDA chelating lithium. Double insertion of tBuNCO and (adventitious) oxygen gives a dimer with a (LiO)2 central core involving the latter source. Insertion of less bulky (iPrNCO) gives a dimer with dimerisation through the C=O bonds of the emergent secondary amide function.

Development of Simplified and Efficient Sample Preparation Methods for the Analysis of Problem Material within the Diesel Fuel Delivery System.

A new approach for the analysis of diesel engine fuel filters has been developed. This method involves minimal to no sample preparation, allowing rapid and unbiased analysis of diesel fuel filters. In recent years, diesel fuel filter plugging incidences have increased in parallel with changing emissions legislation. Fuel filter blockages can result in increased emissions, reduced efficiency, and engine failure. It is not fully understood why fuel filter blockages occur; as a result, there has been an international increase in research into the cause of fuel filter plugging. The method discussed in this paper utilizes a thermal desorption (TD) style sample introduction technique that can be used in conjunction with gas chromatography-mass spectrometry (GC-MS) and presents a fast, simple, and more sustainable approach to the analysis of fuel filters. When required, an efficient and straightforward sample cleanup process was developed and was used to simplify and improve confidence in the data identification and assignment; this method is up to three orders of magnitude faster than some procedures adopted in the literature. Further complementary analytical techniques, such as ultrahigh-performance supercritical fluid chromatography-mass spectrometry (UHPSFC-MS) and high-resolution GC-MS, were used to access additional sample-specific information. This new approach has been successful in the identification of problematic materials deposited on blocked fuel filters, concurrent with recent research. This information can aid in the development of mitigation strategies to combat fuel filter plugging.

Spatially Resolved Molecular Compositions of Insoluble Multilayer Deposits Responsible for Increased Pollution from Internal Combustion Engines.

Internal combustion engines are used heavily in diverse applications worldwide. Achieving the most efficient operation is key to improving air quality as society moves to a decarbonized energy system. Insoluble deposits that form within internal combustion engine components including fuel injectors and filters negatively impact CO2 and pollutant emissions. Understanding the composition, origins, and formation mechanisms of these complex materials will be key to their mitigation however, previous attempts only afforded nondiagnostic chemical assignments and limited knowledge toward this. Here, we uncover the identity and spatial distribution of molecular species from a gasoline direct injector, diesel injector, and filter deposit in situ using a new hyphenation of secondary ion mass spectrometry and the state-of-the-art Orbitrap mass analyzer (3D OrbiSIMS) and elemental analysis. Through a high mass resolving power and tandem MS we unambiguously uncovered the identity, distribution, and origin of species including alkylbenzyl sulfonates and provide evidence of deposit formation mechanisms including formation of longer chain sulfonates at the gasoline deposit's surface as well as aromatization to form polycyclic aromatic hydrocarbons up to C66H20, which were prevalent in the lower depth of this deposit. Inorganic salts contributed significantly to the diesel injector deposit throughout its depth, suggesting contamination over multiple fueling cycles. Findings will enable several strategies to mitigate these insoluble materials such as implementing stricter worldwide fuel specifications, modifying additives with adverse reactivity, and synthesizing new fuel additives to solubilize deposits in the engine, thereby leading to less polluting vehicles.

Diverse outcomes of CO2 fixation using alkali metal amides including formation of a heterobimetallic lithium-sodium carbamato-anhydride via lithium-sodium bis-hexamethyldisilazide.

Fixation of CO2 by lithium amides derived from pyrrole and diisopropylamine generates a lithium carbamate polymer and dodecamer respectively. Moving to lithium-sodium hexamethyldisilazide produces a more complicated, intriguing reaction, where unusually the bimetallic composition is maintained in the product but its composition contains both carbamato and anhydride functionalities.

Persulfate injection into a gasoline source zone.

One pore volume of unactivated sodium persulfate was delivered into an emplaced gasoline residual source zone at CFB Borden. Concentrations of inorganic species (S2O8(2-), SO4(2-), Na(+), dissolved inorganic carbon (DIC)) and selected gasoline compounds (benzene, toluene, ethylbenzene, xylenes, trimethylbenzenes and naphthalene) were monitored across a transect equipped with 90 multilevel sampling points for >10months post-injection. Mass loading (M˙) of compounds constructed from the transect data was used for assessment purposes. Breakthrough of inorganic species was observed when the injection slug crossed the monitoring transect. An increase in [Formula: see text] indicated persulfate consumption during oxidation of gasoline compounds or degradation due to the interaction with aquifer materials. M˙DIC increased by >100% suggesting some mineralization of gasoline compounds during treatment. Mass loading for all the monitored gasoline compounds reduced by 46 to 86% as the inorganic slug crossed the monitoring transect. The cumulative mass discharge across the monitoring transect was 19 to 58% lower than that expected without persulfate injection. After the inorganic injection slug was flushed from the source zone a partial rebound (40 to 80% of baseline levels) of mass discharge of the monitored gasoline compounds was observed. The ensemble of data collected provides insight into the fate and transport of the injected persulfate solution, and the accompanying treatment of a gasoline the source zone.

Unilateral pulmonary artery aplasia in a pregnant patient.

Unilateral pulmonary artery aplasia is a rare anomaly. Case reports of this condition in pregnant patients are even more uncommon and the best approach to management of such patients is still unclear. We report a patient who presented with a history of dyspnea, chest pain, and hemoptysis. Imaging established the diagnosis in a newly pregnant female. Management of the pulmonary artery aplasia patient in pregnancy requires prospective evaluation of pulmonary hypertension.

Estimating contaminant mass discharge: a field comparison of the multilevel point measurement and the integral pumping investigation approaches and their uncertainties.

In this field study, two approaches to assess contaminant mass discharge were compared: the sampling of multilevel wells (MLS) and the integral groundwater investigation (or integral pumping test, IPT) that makes use of the concentration-time series obtained from pumping wells. The MLS approached used concentrations, hydraulic conductivity and gradient rather than direct chemical flux measurements, while the IPT made use of a simplified analytical inversion. The two approaches were applied at a control plane located approximately 40m downgradient of a gasoline source at Canadian Forces Base Borden, Ontario, Canada. The methods yielded similar estimates of the mass discharging across the control plane. The sources of uncertainties in the mass discharge in each approach were evaluated, including the uncertainties inherent in the underlying assumptions and procedures. The maximum uncertainty of the MLS method was about 67%, and about 28% for the IPT method in this specific field situation. For the MLS method, the largest relative uncertainty (62%) was attributed to the limited sampling density (0.63 points/m(2)), through a novel comparison with a denser sampling grid nearby. A five-fold increase of the sampling grid density would have been required to reduce the overall relative uncertainty for the MLS method to about the same level as that for the IPT method. Uncertainty in the complete coverage of the control plane provided the largest relative uncertainty (37%) in the IPT method. While MLS or IPT methods to assess contaminant mass discharge are attractive assessment tools, the large relative uncertainty in either method found for this reasonable well monitored and simple aquifer suggests that results in more complex plumes in more heterogeneous aquifers should be viewed with caution.

Persistence of persulfate in uncontaminated aquifer materials.

Batch and stop-flow column experiments were performed to estimate persulfate decomposition kinetic parameters in the presence of seven well-characterized aquifer materials. Push-pull tests were conducted in a sandy aquifer to represent persulfate decomposition under in situ conditions. The decomposition of persulfate followed a first-order rate law for all aquifer materials investigated. Reaction rate coefficients (k(obs)) increased by an order of magnitude when persulfate concentration was reduced from 20 g/L to 1 g/L, due to ionic strength effects. The column experiments yielded higher k(obs) than batch experiments due to the lower oxidant to solids mass ratio. The kinetic model developed from the batch test data was able to reproduce the observed persulfate temporal profiles from the push-pull tests. The estimated k(obs) indicate that unactivated persulfate is a persistent oxidant for the range of aquifer materials explored with half-lives ranging from 2 to 600 d.