Dynamical Equilibrium between Brønsted and Lewis Sites in Zeolites: Framework-Associated Octahedral Aluminum.

While the structures of Brønsted acid sites (BAS) in zeolites are well understood, those of Lewis acid sites (LAS) remain an active area of investigation. Under hydrated conditions, the reversible formation of framework-associated octahedral aluminum has been observed in zeolites in the acidic form. However, the structure and formation mechanisms are currently unknown. In this work, combined experimental 27 Al NMR spectroscopy and computational data reveal for the first time the details of the zeolite framework-associated octahedral aluminium. The octahedral LAS site becomes kinetically allowed and thermodynamically stable under wet conditions in the presence of multiple nearby BAS sites. The critical condition for the existence of such octahedral LAS appears to be the availability of three protons: at lower proton concentration, either by increasing the Si/Al or by ion-exchange to non-acidic form, the tetrahedral BAS becomes thermodynamically more stable. This work resolves the question about the nature and reversibility of framework-associated octahedral aluminium in zeolites.

Structure and Framework Association of Lewis Acid Sites in MOR Zeolite.

Zeolites, although key materials used in industrial processes, remain poorly understood on a molecular level despite their well-defined crystal lattices. In fact, obtaining a direct spectroscopic signatures and resolving the structure of Lewis acid sites (LAS) has remained a challenge. In this work, thanks to 1D and 2D 1H, 15N, and 27Al MAS NMR spectroscopy, carried out at different temperatures (from 298 down to 107 K), we were able to obtain the NMR spectroscopic signatures of LAS and Brønsted acid sites (BAS) in mordenite zeolite in the presence and the absence of adsorbed pyridine (Py). Combined with DFT modeling, this information enabled the structure of LAS to be revealed, namely (≡SiO)3Al sites interacting with pyridine, thus indicating that the corresponding base-free framework-associated sites are pseudo tricoordinated Al sites, namely tricoordinated Al sites interacting with an additional coordinated adjacent siloxane bridge. With this information in hand, we propose a molecular-level understanding on how the AlIV and AlVI framework and framework-associated sites evolve upon dehydration and exposure to Py into BAS and LAS, and their associated Py adducts. By measuring and analyzing the changes in quadrupolar coupling constants (CQ) that reflect electrical charge distribution around the nuclei, we further show that the lower CQ values observed at 298 K are due to residual dynamics that makes the electric field around aluminum nuclei more symmetric. Thus, NMR spectroscopic signatures of 27Al greatly vary with temperature; this information illustrates the importance of accounting for the temperature effect when confronting experimental and calculated CQ values of the corresponding aluminum sites in zeolites in order to obtain accurate structural assessment.

Towards a better understanding of Lewis acidic aluminium in zeolites.

Zeolites are a class of materials that are of great relevance for industrial catalysis. Several fundamental questions relating to the structure and role of the Lewis acid sites in these materials remain unanswered. Proposals for the origin of such species can broadly be classified into three categories, which have distinct structures: extra-framework, framework-associated and framework aluminium. In this Perspective, we review each of these proposals and proceed to analyse their suitability to understand experimental results. Contrary to traditional belief, the number of Lewis acid sites does not always correlate to extra-framework aluminium content. As a result, we highlight that the terms 'extra-framework' and 'framework-associated' aluminium should be used with caution. We propose how the usage of different characterization techniques can enable the closure of knowledge gaps concerning the strength, multiplicity, localization and structure of catalytically active Lewis acid sites in zeolites.

Esterification Product Protection Strategies for Direct and Selective Methane Conversion.

A scale-flexible process for the direct and selective oxidation of methane to primary oxygenates is of great interest, however, a commercially feasible approach has yet to be realized due to a number of challenges. Low product yields imposed by a well-established selectivity-conversion limit are particularly burdensome for direct methane-to-methanol chemistry. One strategy that has emerged to break out of this limit is the in situ esterification of produced methanol to the more oxidation-resistant methyl ester. However, these methaneto-methyl-ester approaches still elude commercialization despite their unprecedented high yields. Herein, we outline some of the key barriers that hinder the commercial prospects of this otherwise promising route for highyield direct catalytic methane conversion, including extremely corrosive reagents, homogeneous catalysts, and inviable oxidants. We then highlight directions to address these challenges while maintaining the characteristic high performance of these systems. These discussions support the efficacy of product protection strategies for the direct, selective oxidation of methane and encourage future work in developing creative solutions to merge this promising chemistry with more practical industrial requirements.

Heterogeneously Catalyzed Aerobic Oxidation of Methane to a Methyl Derivative.

A promising strategy to break through the selectivity-conversion limit of direct methane conversion to achieve high yields is the protection of methanol via esterification to a more stable methyl ester. We present an aerobic methane-to-methyl-ester approach that utilizes a highly dispersed, cobalt-containing solid catalyst, along with significantly more favorable reaction conditions compared to existing homogeneously-catalyzed approaches (e.g. diluted acid, O2 oxidant, moderate temperature and pressure). The trifluoroacetic acid medium is diluted (<25 wt %) with an inert fluorous co-solvent that can be recovered after the separation of the methyl trifluoroacetate via liquid-liquid extraction at ambient conditions. Silica-supported cobalt catalysts are highly active in this system, with competitive yields and turnovers in comparison to known aerobic transition metal-based catalytic systems.

Ferulic acid attenuates arsenic-induced cardiotoxicity in rats.

Arsenic (As), a potent environmental toxin, causes cardiac functional impairments. Ferulic acid (FA), a ubiquitous dietary hydroxycinnamate, exerts beneficial effects on human health. Hence, the present study investigated the effect of FA on myocardial oxidative stress parameters, ATP level, the status of cardiac cytoskeleton intermediate filaments-desmin and vimentin, and AMPK signaling proteins in As-intoxicated rats. Wistar rats were administered orally with FA-40 mg/kg and As-5 mg/kg alone and in combination for 30 days. Myocardial As content, serum cardiac marker enzyme activities including creatine kinase-isoenzyme, lactate dehydrogenase, and aspartate aminotransferase were increased in As-exposed rats. An accumulation of myocardial oxidants such as reactive oxygen species, lipid peroxidation, nitric oxide, protein carbonyl content, and histological aberrations was observed. A significant decrease of myocardial antioxidants comprises superoxide dismutase, catalase, glutathione peroxidase, reduced glutathione, and ascorbic acid and declined expression of desmin and vimentin was noted. Impaired energy signaling molecules AMPKα (Thr172), AMPKß1/2 (Ser108), ACC (Ser79), and intracellular myocardial ATP depletion were observed in As-intoxicated animals. FA attenuates As-induced cardiac dysfunction by restoring the expression of intermediate filaments and AMPK proteins. Based on the above findings, FA treatment could be used as a novel therapeutic against As-induced cardiac dysfunction.

The Direct Catalytic Oxidation of Methane to Methanol-A Critical Assessment.

Despite the large number of disparate approaches for the direct selective partial oxidation of methane, none of them has translated into an industrial process. The oxidation of methane to methanol is a difficult, but intriguing and rewarding, task as it has the potential to eliminate the prevalent natural gas flaring by providing novel routes to its valorization. This Review considers the synthesis of methanol and methanol derivatives from methane by homogeneous and heterogeneous pathways. By establishing the severe limitations related to the direct catalytic synthesis of methanol from methane, we highlight the vastly superior performance of systems which produce methanol derivatives or incorporate specific measures, such as the use of multicomponent catalysts to stabilize methanol. We thereby identify methanol protection as being indispensable for future research on homogeneous and heterogeneous catalysis.

Lithium-nitrogen-hydrogen systems for ammonia synthesis: exploring a more efficient pathway using lithium nitride-hydride.

Ammonia synthesis chemistry with lithium-nitrogen-hydrogen materials is largely confined to pathways involving lithium hydride and lithium imide. Herein, we explore an alternate pathway featuring lithium nitride-hydride that shows more favorable characteristics from an activity, synthesis and cyclability perspective.

Facilitating green ammonia manufacture under milder conditions: what do heterogeneous catalyst formulations have to offer?

Ammonia production is one of the largest industrial processes, and is currently responsible for over 1.5% of global greenhouse gas emissions. Decarbonising this process, yielding 'green ammonia', is critical not only for sustainable fertilizer production, but also to unlocking ammonia's potential as a zero-carbon fuel and hydrogen store. In this perspective, we critically assess the role of cutting-edge heterogeneous catalysts to facilitate milder ammonia synthesis conditions that will help unlock cheaper, smaller-scale, renewables-coupled ammonia production. The highly-optimised performance of catalysts under the high temperatures and pressures of the Haber-Bosch process stands in contrast to the largely mediocre activity levels reported at lower temperatures and pressures. We identify the recent advances in catalyst design that help overcome the sluggish kinetics of nitrogen activation under these conditions and undertake a categorized analysis of improved activity achieved in a range of heterogeneous catalysts. Building on these observations, we develop a 'catalyst efficiency' analysis which helps uncover the success of a holistic approach - one that addresses the issues of nitrogen activation, hydrogenation of adsorbed nitrogen species, and engineering of materials to maximize the utilization of active sites - for achieving the elusive combination of high-activity, low-temperature formulations. Furthermore, we present a discussion on the industrial considerations to catalyst development, emphasising the importance of catalyst lifetime in addition to catalyst activity. This assessment is critical to ensuring that high productivities can translate into real advances in commercial ammonia synthesis.

On the location of Lewis acidic aluminum in zeolite mordenite and the role of framework-associated aluminum in mediating the switch between Brønsted and Lewis acidity.

Lewis acidic aluminum in zeolites, particularly acidity that is inherent to the framework, is an indeterminate concept. A fraction of framework aluminum changes geometry to octahedral coordination in the proton form of zeolite mordenite. Such octahedrally coordinated aluminum is the precursor of a Lewis acid site and its formation is accompanied by a loss in Brønsted acidity. Herein, we show that such Lewis acid sites have a preferred location in the pore structure of mordenite. A greater proportion of these Lewis acid sites resides in the side-pockets than in the main channel. By reverting the octahedrally coordinated aluminum back to a tetrahedral geometry, the corresponding Brønsted acid sites are restored with a concomitant loss in the ability to form Lewis acid sites. Thereby, reversible octahedral-tetrahedral aluminum coordination provides a means to indirectly switch between Lewis and Brønsted acidity. This phenomenon is unique to Lewis acidity that is inherent to the framework, thereby distinguishing it from Lewis acidity originating from extra-framework species. Furthermore, the transformation of framework aluminum into octahedral coordination is decoupled from the generation of distorted tetrahedrally coordinated aluminum, where the latter gives rise to the IR band at 3660 cm-1 in the OH stretching region.

Door to balloon time in patients presenting with acute ST elevation myocardial infarction and time factors influencing it; an observational study from a tertiary care teaching hospital in India.

The objective of this prospective observational study was to assess the door-to-balloon time (D2B), in acute ST-segment elevation myocardial infarction (STEMI) patients and the time factors influencing it. The following timeframes were measured during the study: ED to ECG time, ED to coronary care unit time (ED2CCU), consent time, post-consent to balloon time (POSTCONSENT2B) and D2B. Effective D2B was 54 ± 12.2 min. Of the dependent variables, D2B had a strong positive correlation (ρ = 0.903) with consent time. This study sheds light on consent time a previously unrecognized entity as a significantly influencing factor for the D2B time.

Primary Fusiform Superior Vena Cava Aneurysm.

Superior vena cava (SVC) aneurysms are rare mediastinal vascular lesions. We report a case of a 42-year-old female, who presented to the outpatient department with features suggestive of lower respiratory tract infection. Chest X-ray showed abnormal contour and widening of right border of mediastinum. Computed tomography (CT) thorax revealed fusiform aneurysmal ectasia of SVC measuring 4.5 × 5.5 × 8.9 cm without internal thrombosis or dissecting flap. Management options include observation with follow-up and in some cases anticoagulation and surgical excision may be considered. The general consensus is that fusiform variety can be managed conservatively in view of the low risk of complications. The saccular aneurysms may need to be managed with anticoagulation therapy or surgically in view of the possible risk for thrombus formation and pulmonary embolism. Since in our case it was an asymptomatic primary fusiform SVC aneurysm, patient was advised for conservative management and follow-up.