Promoting active site renewal in heterogeneous olefin metathesis catalysts.

As an atom-efficient strategy for the large-scale interconversion of olefins, heterogeneously catalysed olefin metathesis sees commercial applications in the petrochemical, polymer and speciality chemical industries1. Notably, the thermoneutral and highly selective cross-metathesis of ethylene and 2-butenes1 offers an appealing route for the on-purpose production of propylene to address the C3 shortfall caused by using shale gas as a feedstock in steam crackers2,3. However, key mechanistic details have remained ambiguous for decades, hindering process development and adversely affecting economic viability4 relative to other propylene production technologies2,5. Here, from rigorous kinetic measurements and spectroscopic studies of propylene metathesis over model and industrial WOx/SiO2 catalysts, we identify a hitherto unknown dynamic site renewal and decay cycle, mediated by proton transfers involving proximal Brønsted acidic OH groups, which operates concurrently with the classical Chauvin cycle. We show how this cycle can be manipulated using small quantities of promoter olefins to drastically increase steady-state propylene metathesis rates by up to 30-fold at 250 °C with negligible promoter consumption. The increase in activity and considerable reduction of operating temperature requirements were also observed on MoOx/SiO2 catalysts, showing that this strategy is possibly applicable to other reactions and can address major roadblocks associated with industrial metathesis processes.

Origin of Reactivity Trends of an Elusive Metathesis Intermediate from NMR Chemical Shift Analysis of Surrogate Analogues.

Olefin metathesis has become an efficient tool in synthetic organic chemistry to build carbon-carbon bonds, thanks to the development of Grubbs- and Schrock-type catalysts. Olefin coordination, a key and often rate-determining elementary step for d0 Schrock-type catalysts, has been rarely explored due to the lack of accessible relevant molecular analogues. Herein, we present a fully characterized surrogate of this key olefin-coordination intermediate, namely, a cationic d0 tungsten oxo-methylidene complex bearing two N-heterocyclic carbene ligands─[WO(CH2)Cl(IMes)2](OTf) (1) (IMes = 1,3-dimesitylimidazole-2-ylidene, OTf-triflate counteranion), resulting in a trigonal bipyramidal (TBP) geometry, along with its neutral octahedral analogue [WO(CH2)Cl2(IMes)2] (2)─and an isostructural oxo-methylidyne derivative [WO(CH)Cl(IMes)2] (3). The analysis of their solid-state 13C and 183W MAS NMR signatures, along with computed 17O NMR parameters, helps to correlate their electronic structures with NMR patterns and evidences the importance of the competition among the three equatorial ligands in the TBP complexes. Anchored on experimentally obtained NMR parameters for 1, computational analysis of a series of olefin coordination intermediates highlights the interplay between σ- and π-donating ligands in modulating their stability and further paralleling their reactivity. NMR spectroscopy descriptors reveal the origin for the advantage of the dissymmetry in σ-donating abilities of ancillary ligands in Schrock-type catalysts: weak σ-donors avoid the orbital-competition with the oxo ligand upon formation of a TBP olefin-coordination intermediate, while stronger σ-donors compromise M≡O triple bonding and thus render olefin coordination step energy demanding.

Tailored Lewis Acid Sites for High-Temperature Supported Single-Molecule Magnetism.

Generating or even retaining slow magnetic relaxation in surface immobilized single-molecule magnets (SMMs) from promising molecular precursors remains a great challenge. Illustrative examples are organolanthanide compounds that show promising SMM properties in molecular systems, though surface immobilization generally diminishes their magnetic performance. Here, we show how tailored Lewis acidic Al(III) sites on a silica surface enable generation of a material with SMM characteristics via chemisorption of (Cpttt)2DyCl ((Cpttt)- = 1,2,4-tri(tert-butyl)-cyclopentadienide). Detailed studies of this system and its diamagnetic Y analogue indicate that the interaction of the metal chloride with surface Al sites results in a change of the coordination sphere around the metal center inducing for the dysprosium-containing material slow magnetic relaxation up to 51 K with hysteresis up to 8 K and an effective energy barrier (Ueff) of 449 cm-1, the highest reported thus far for a supported SMM.

NMR Signatures and Electronic Structure of Ti Sites in Titanosilicalite-1 from Solid-State 47/49Ti NMR Spectroscopy.

Although titanosilicalite-1 (TS-1) is among the most successful oxidation catalysts used in industry, its active site structure is still debated. Recent efforts have mostly focused on understanding the role of defect sites and extraframework Ti. Here, we report the 47/49Ti signature of TS-1 and molecular analogues [Ti(OTBOS)4] and [Ti(OTBOS)3(OiPr)] using novel MAS CryoProbe to enhance the sensitivity. While the dehydrated TS-1 displays chemical shifts similar to those of molecular homologues, confirming the tetrahedral environment of Ti consistent with X-ray absorption spectroscopy, it is associated with a distribution of larger quadrupolar coupling constants, indicating an asymmetric environment. Detailed computational studies on cluster models highlights the high sensitivity of the NMR signatures (chemical shift and quadrupolar coupling constant) to small local structural changes. These calculations show that, while it will be difficult to distinguish mono- vs dinuclear sites, the sensitivity of the 47/49Ti NMR signature should enable distinguishing the Ti location among specific T site positions.

Active Site Descriptors from 95Mo NMR Signatures of Silica-Supported Mo-Based Olefin Metathesis Catalysts.

The olefin metathesis activity of silica-supported molybdenum oxides depends strongly on metal loading and preparation conditions, indicating that the nature and/or amounts of the active sites vary across compositionally similar catalysts. This is illustrated by comparing Mo-based (pre)catalysts prepared by impregnation (2.5-15.6 wt % Mo) and a model material (2.3 wt % Mo) synthesized via surface organometallic chemistry (SOMC). Analyses of FTIR, UV-vis, and Mo K-edge X-ray absorption spectra show that these (pre)catalysts are composed predominantly of similar isolated Mo dioxo sites. However, they exhibit different reaction properties in both liquid and gas-phase olefin metathesis with the SOMC-derived catalyst outperforming a classical catalyst of a similar Mo loading by ×1.5-2.0. Notably, solid-state 95Mo NMR analyses leveraging state-of-the-art high-field (28.2 T) measurement conditions resolve four distinct surface Mo dioxo sites with distributions that depend on the (pre)catalyst preparation methods. The intensity of a specific deshielded 95Mo NMR signal, which is most prominent in the SOMC-derived catalyst, is linked to reducibility and catalytic activity. First-principles calculations show that 95Mo NMR parameters directly manifest the local strain and coordination environment: acute (SiO-Mo(O)2-OSi) angles and low coordination numbers at Mo lead to highly deshielded 95Mo chemical shifts and small quadrupolar coupling constants, respectively. Natural chemical shift analyses relate the 95Mo NMR signature of strained species to low LUMO energies, which is consistent with their high reducibility and corresponding reactivity. The 95Mo chemical shifts of supported Mo dioxo sites are thus linked to their specific electronic structures, providing a powerful descriptor for their propensity toward reduction and formation of active sites.

Lithium Promotes Acetylide Formation on MgO During Methane Coupling Under Non-Oxidative Conditions.

A prototypical material for the oxidative coupling of methane (OCM) is Li/MgO, for which Li is known to be essential as a dopant to obtain high C2 selectivities. Herein, Li/MgO is demonstrated to be an effective catalyst for non-oxidative coupling of methane (NOCM). Moreover, the presence of Li is shown to favor the formation of magnesium acetylide (MgC2 ), while pure MgO promotes coke formation as evidenced by solid-state 13 C NMR, thus indicating that Li promotes C-C bond formation. Metadynamic simulations of the carbon mobility in MgC2 and Li2 C2 at the density functional theory (DFT) level show that carbon easily diffuses as a C2 unit at 1000 °C. These insights suggest that the enhanced C2 selectivity for Li-doped MgO is related to the formation of Li and Mg acetylides.

Classifying and Understanding the Reactivities of Mo-Based Alkyne Metathesis Catalysts from 95Mo NMR Chemical Shift Descriptors.

The most active alkyne metathesis catalysts rely on well-defined Mo alkylidynes, X3Mo≡CR (X = OR), in particular the recently developed canopy catalyst family bearing silanolate ligand sets. Recent efforts to understand catalyst reactivity patterns have shown that NMR chemical shifts are powerful descriptors, though previous studies have mostly focused on ligand-based NMR descriptors. Here, we show in the context of alkyne metathesis that 95Mo chemical shift tensors encode detailed information on the electronic structure of these catalysts. Analysis by first-principles calculations of 95Mo chemical shift tensors extracted from solid-state 95Mo NMR spectra shows a direct link of chemical shift values with the energies of the HOMO and LUMO, two molecular orbitals involved in the key [2 + 2]-cycloaddition step, thus linking 95Mo chemical shifts to reactivity. In particular, the 95Mo chemical shifts are driven by ligand electronegativity (σ-donation) and electron delocalization through Mo-O π interactions, thus explaining the reactivity patterns of the silanolate canopy catalysts. These results further motivate exploration of transition metal NMR signatures and their relationships to electronic structure and reactivity.

Leveraging Surface Siloxide Electronics to Enhance the Relaxation Properties of a Single-Molecule Magnet.

Single-molecule magnets (SMMs) hold promise for unmatched information storage density as well as for applications in quantum computing and spintronics. To date, the most successful SMMs have been organometallic lanthanide complexes. However, their surface immobilization, one of the requirements for device fabrication and commercial application, remains challenging due to the sensitivity of the magnetic properties to small changes in the electronic structure of the parent SMM. Thus, finding controlled approaches to SMM surface deposition is a timely challenge. In this contribution we apply the concept of isolobality to identify siloxides present at the surface of partially dehydroxylated silica as a suitable replacement for archetypal ligand architectures in organometallic SMMs. We demonstrate theoretically and experimentally that isolated siloxide anchoring sites not only enable successful immobilization but also lead to a 2 orders of magnitude increase in magnetization relaxation times.

Inflammation after spinal cord injury: a review of the critical timeline of signaling cues and cellular infiltration.

Traumatic spinal cord injury (SCI) is a devastating neurological condition that results in a loss of motor and sensory function. Although extensive research to develop treatments for SCI has been performed, to date, none of these treatments have produced a meaningful amount of functional recovery after injury. The primary injury is caused by the initial trauma to the spinal cord and results in ischemia, oxidative damage, edema, and glutamate excitotoxicity. This process initiates a secondary injury cascade, which starts just a few hours post-injury and may continue for more than 6 months, leading to additional cell death and spinal cord damage. Inflammation after SCI is complex and driven by a diverse set of cells and signaling molecules. In this review, we utilize an extensive literature survey to develop the timeline of local immune cell and cytokine behavior after SCI in rodent models. We discuss the precise functional roles of several key cytokines and their effects on a variety of cell types involved in the secondary injury cascade. Furthermore, variations in the inflammatory response between rats and mice are highlighted. Since current SCI treatment options do not successfully initiate functional recovery or axonal regeneration, identifying the specific mechanisms attributed to secondary injury is critical. With a more thorough understanding of the complex SCI pathophysiology, effective therapeutic targets with realistic timelines for intervention may be established to successfully attenuate secondary damage.

Boosting the Metathesis Activity of Molybdenum Oxo Alkylidenes by Tuning the Anionic Ligand σ Donation.

The catalytic performances of molecular and silica-supported molybdenum oxo alkylidene species bearing anionic O ligands [ORF9, OTPP, OHMT - where ORF9 = OC(CF3)3, OTPP = 2,3,5,6-tetraphenylphenoxy, OHMT = hexamethylterphenoxy] with different σ-donation abilities and sizes are evaluated in the metathesis of both internal and terminal olefins. Here, we show that the presence of the anionic nonafluoro-tert-butoxy X ligand in Mo(O){═CH-4-(MeO)C6H4}(THF)2{X}2 (1; X = ORF9) significantly increases the catalytic performances in the metathesis of both terminal and internal olefins. Its silica-supported equivalent displays slightly lower activity, albeit with improved stability. In sharp contrast, the molecular complexes with large aryloxy anionic X ligands show little activity, whereas the activity of the corresponding silica-supported systems is greatly improved, illustrating that surface siloxy groups are significantly smaller anionic ligands. Of all of the systems, compound 1 stands out because of its unique high activity for both terminal and internal olefins. Density functional theory modeling indicates that the ORF9 ligand is ideal in this series because of its weak σ-donating ability, avoiding overstabilization of the metallacyclobutane intermediates while keeping low barriers for [2 + 2] cycloaddition and turnstile isomerization.

A modified diet to support conservation of the Atala hairstreak butterfly (Eumaeus atala Poey).

Raising insects in a laboratory for release into the wild is a common conservation practice, but maintaining breeding colonies year-round can be limited by seasonal food availability. Food availability is particularly challenging for insects which depend on specific host plants. For example, our early efforts to rear the imperiled Atala hairstreak butterfly (Eumaeus atala Poey) resulted in colony failure during winter due to lack of food. To overcome this barrier, we developed a modified freeze-dried host plant diet to support the colony. The diet consisted of reconstituted freeze-dried leaves and stems from fresh-growth coontie (Zamia integrifolia), the host plant for the Atala butterflies. We fed larvae less than 9 mm on this freeze-dried diet and transferred them to live coontie plants after they were more than 9 mm. We reared a colony of Atala butterflies using these methods for 859 days, resulting in more than 3400 animals released into the wild. Comparing colony counts during that time period to the 548 days we reared them without modified freeze-dried diet showed a clear benefit in using freeze-dried diet. A growth trial (N = 40) of larvae fed on only freeze-dried diet compared to larvae fed on fresh coontie cuttings found no significant difference in larval or pupal development between groups (p = 0.71 and p = 0.47, respectively). We, therefore, conclude that the freeze-dried diet provided an appropriate alternative for Atala colonies when fresh growth from the host plant is unavailable, and we recommend use of this technique for raising other host plant-dependent insect species of conservation concern.

Selective N-Terminal BET Bromodomain Inhibitors by Targeting Non-Conserved Residues and Structured Water Displacement*.

Bromodomain and extra-terminal (BET) family proteins, BRD2-4 and T, are important drug targets; however, the biological functions of each bromodomain remain ill-defined. Chemical probes that selectively inhibit a single BET bromodomain are lacking, although pan inhibitors of the first (D1), and second (D2), bromodomain are known. Here, we develop selective BET D1 inhibitors with preferred binding to BRD4 D1. In competitive inhibition assays, we show that our lead compound is 9-33 fold selective for BRD4 D1 over the other BET bromodomains. X-ray crystallography supports a role for the selectivity based on reorganization of a non-conserved lysine and displacement of an additional structured water in the BRD4 D1 binding site relative to our prior lead. Whereas pan-D1 inhibitors displace BRD4 from MYC enhancers, BRD4 D1 inhibition in MM.1S cells is insufficient for stopping Myc expression and may lead to its upregulation. Future analysis of BRD4 D1 gene regulation may shed light on differential BET bromodomain functions.

Crystallization of Mordenite Platelets using Cooperative Organic Structure-Directing Agents.

Organic structure-directing agents (OSDAs) are exploited in the crystallization of microporous materials to tailor the physicochemical properties of the resulting zeolite for applications ranging from separations to catalysis. The rational design of these OSDAs often entails the identification of molecules with a geometry that is commensurate with the channels and cages of the target zeolite structure. Syntheses tend to employ only a single OSDA, but there are a few examples where two or more organics operate synergistically to yield a desired product. Using a combination of state-of-the-art characterization techniques and molecular modeling, we show that the coupling of N,N,N-trimethyl-1,1-adamantammonium and 1,2-hexanediol, each yielding distinct zeolites when used alone, results in the cooperative direction of a third structure, HOU-4, with the mordenite framework type (MOR). Rietveld refinement using synchrotron X-ray diffraction data reveals the spatial arrangement of the organics in the HOU-4 crystals, with amines located in the large channels and alcohols oriented in the side pockets lining the one-dimensional pores. These results are in excellent agreement with molecular dynamics calculations, which predict similar spatial distributions of organics with an energetically favorable packing density that agrees with experimental measurements of OSDA loading, as well as with solid-state two-dimensional 27Al{29Si}, 27Al{1H}, and 13C{1H} NMR correlation spectra, which establish the proximities and interactions of occluded OSDAs. A combination of high-resolution transmission electron microscopy and atomic force microscopy is used to quantify the size of the HOU-4 crystals, which exhibit a platelike morphology, and to index the crystal facets. Our findings reveal that the combined OSDAs work in tandem to produce ultrathin, nonfaulted HOU-4 crystals that exhibit improved catalytic activity for cumene cracking in comparison to mordenite crystals prepared via conventional syntheses. This novel demonstration of cooperativity highlights the potential possibilities for expanding the use of dual structure-directing agents in zeolite synthesis.

Publisher Correction: A molecular cross-linking approach for hybrid metal oxides.

In the version of this Article originally published, Liban M. A. Saleh was incorrectly listed as Liban A. M. Saleh due to a technical error. This has now been amended in all online versions of the Article.

A molecular cross-linking approach for hybrid metal oxides.

There is significant interest in the development of methods to create hybrid materials that transform capabilities, in particular for Earth-abundant metal oxides, such as TiO2, to give improved or new properties relevant to a broad spectrum of applications. Here we introduce an approach we refer to as 'molecular cross-linking', whereby a hybrid molecular boron oxide material is formed from polyhedral boron-cluster precursors of the type [B12(OH)12]2-. This new approach is enabled by the inherent robustness of the boron-cluster molecular building block, which is compatible with the harsh thermal and oxidizing conditions that are necessary for the synthesis of many metal oxides. In this work, using a battery of experimental techniques and materials simulation, we show how this material can be interfaced successfully with TiO2 and other metal oxides to give boron-rich hybrid materials with intriguing photophysical and electrochemical properties.

Biochemical characterization of the catecholaldehyde reactivity of L-carnosine and its therapeutic potential in human myocardium.

Oxidative deamination of norepinephrine (NE) and dopamine (DA) by monoamine oxidase (MAO) generates the catecholaldehydes 3,4-dihydroxyphenylglycolaldehyde (DOPEGAL) and 3,4-dihydroxyphenylacetaldehyde (DOPAL), respectively, and H2O2. Catecholaldehydes are highly reactive electrophiles that have been implicated as causal factors in the etiology of neurodegenerative diseases and cardiac injury from ischemia and diabetes. The reactivity of both catechol and aldehyde groups enables the catecholaldehdyes to cross-link proteins and other biological molecules. Carnosine is a ß-alanyl-histidine dipeptide found in millimolar concentrations in brain and myocardium. It is well known to detoxify aldehydes formed from oxidized lipids and sugars, yet the reactivity of carnosine with catecholaldehydes has never been reported. Here, we investigated the ability of carnosine to form conjugates with DOPAL and DOPEGAL. Both catecholaldehydes were highly reactive towards L-cysteine (L-Cys), as well as carnosine; however, glutathione (GSH) showed essentially no reactivity towards DOPAL. In contrast, GSH readily reacted with the lipid peroxidation product 4-hydroxy-2-nonenal (4HNE), while carnosine showed low reactivity to 4HNE by comparison. To determine whether carnosine mitigates catecholaldehyde toxicity, samples of atrial myocardium were collected from patients undergoing elective cardiac surgery. Using permeabilized myofibers prepared from this tissue, mitochondrial respiration analysis revealed a concentration-dependent decrease in ADP-stimulated respiration with DOPAL. Pre-incubation with carnosine, but not GSH or L-Cys, significantly reduced this effect (p < 0.05). Carnosine was also able to block formation of catecholaldehyde protein adducts in isolated human cardiac mitochondria treated with NE. These findings demonstrate the unique reactivity of carnosine towards catecholaldehydes and, therefore, suggest a novel and distinct biological role for histidine dipeptides in this detoxification reaction. The therapeutic potential of carnosine in diseases associated with catecholamine-related toxicity is worthy of further examination.

Electrochemically Enhanced Dissolution of Silica and Alumina in Alkaline Environments.

Dissolution of mineral surfaces at asymmetric solid-liquid-solid interfaces in aqueous solutions occurs in technologically relevant processes, such as chemical/mechanical polishing (CMP) for semiconductor fabrication, formation and corrosion of structural materials, and crystallization of materials relevant to heterogeneous catalysis or drug delivery. In some such processes, materials at confined interfaces exhibit dissolution rates that are orders of magnitude larger than dissolution rates of isolated surfaces. Here, the dissolution of silica and alumina in close proximity to a charged gold surface or mica in alkaline solutions of pH 10-11 is shown to depend on the difference in electrostatic potentials of the surfaces, as determined from measurements conducted using a custom-built electrochemical pressure cell and a surface forces apparatus (SFA). The enhanced dissolution is proposed to result from overlap of the electrostatic double layers between the dissimilar charged surfaces at small intersurface separation distances (<1 Debye length). A semiquantitative model shows that overlap of the electric double layers can change the magnitude and direction of the electric field at the surface with the less negative potential, which results in an increase in the rate of dissolution of that surface. When the surface electrochemical properties were changed, the dissolution rates of silica and alumina were increased by up to 2 orders of magnitude over the dissolution rates of isolated compositionally similar surfaces under otherwise identical conditions. The results provide new insights on dissolution processes that occur at solid-liquid-solid interfaces and yield design criteria for controlling dissolution through electrochemical modification, with relevance to diverse technologies.

Multimodal Miniature Surface Forces Apparatus (µSFA) for Interfacial Science Measurements.

Advances in the research of intermolecular and surface interactions result from the development of new and improved measurement techniques and combinations of existing techniques. Here, we present a new miniature version of the surface forces apparatus-the µSFA-that has been designed for ease of use and multimodal capabilities with the retention of the capabilities of other SFA models including accurate measurements of the surface separation distance and physical characterization of dynamic and static physical forces (i.e., normal, shear, and friction) and interactions (e.g., van der Waals, electrostatic, hydrophobic, steric, and biospecific). The small physical size of the µSFA, compared to previous SFA models, makes it portable and suitable for integration into commercially available optical and fluorescence light microscopes, as demonstrated here. The large optical path entry and exit ports make it ideal for concurrent force measurements and spectroscopy studies. Examples of the use of the µSFA in combination with surface plasmon resonance (SPR) and Raman spectroscopy measurements are presented. Because of the short working distance constraints associated with Raman spectroscopy, an interferometric technique was developed and applied to calculate the intersurface separation distance based on Newton's rings. The introduction of the µSFA will mark a transition in SFA usage from primarily physical characterization to concurrent physical characterization with in situ chemical and biological characterization to study interfacial phenomena, including (but not limited to) molecular adsorption, fluid flow dynamics, the determination of surface species and morphology, and (bio)molecular binding kinetics.

Preferential Siting of Aluminum Heteroatoms in the Zeolite Catalyst Al-SSZ-70.

The adsorption and reaction properties of heterogeneous zeolite catalysts (e.g. for catalytic cracking of petroleum, partial oxidation of natural gas) depend strongly on the types and distributions of Al heteroatoms in the aluminosilicate frameworks. The origins of these properties have been challenging to discern, owing in part to the structural complexity of aluminosilicate zeolites. Herein, combined solid-state NMR and synchrotron X-ray powder diffraction analyses show the Al atoms locate preferentially in certain framework sites in the zeolite catalyst Al-SSZ-70. Through-covalent-bond 2D 27 Al{29 Si} J-correlation NMR spectra allow distinct framework Al sites to be identified and their relative occupancies quantified. The analyses show that 94 % of the Al atoms are located at the surfaces of the large-pore interlayer channels of Al-SSZ-70, while only 6 % are in the sub-nm intralayer channels. The selective siting of Al atoms accounts for the reaction properties of catalysts derived from SSZ-70.

Interannual bumble bee abundance is driven by indirect climate effects on floral resource phenology.

Climate change can influence consumer populations both directly, by affecting survival and reproduction, and indirectly, by altering resources. However, little is known about the relative importance of direct and indirect effects, particularly for species important to ecosystem functioning, like pollinators. We used structural equation modelling to test the importance of direct and indirect (via floral resources) climate effects on the interannual abundance of three subalpine bumble bee species. In addition, we used long-term data to examine how climate and floral resources have changed over time. Over 8 years, bee abundances were driven primarily by the indirect effects of climate on the temporal distribution of floral resources. Over 43 years, aspects of floral phenology changed in ways that indicate species-specific effects on bees. Our study suggests that climate-driven alterations in floral resource phenology can play a critical role in governing bee population responses to global change.