A very luminous jet from the disruption of a star by a massive black hole.

Tidal disruption events (TDEs) are bursts of electromagnetic energy that are released when supermassive black holes at the centres of galaxies violently disrupt a star that passes too close1. TDEs provide a window through which to study accretion onto supermassive black holes; in some rare cases, this accretion leads to launching of a relativistic jet2-9, but the necessary conditions are not fully understood. The best-studied jetted TDE so far is Swift J1644+57, which was discovered in γ-rays, but was too obscured by dust to be seen at optical wavelengths. Here we report the optical detection of AT2022cmc, a rapidly fading source at cosmological distance (redshift z = 1.19325) the unique light curve of which transitioned into a luminous plateau within days. Observations of a bright counterpart at other wavelengths, including X-ray, submillimetre and radio, supports the interpretation of AT2022cmc as a jetted TDE containing a synchrotron 'afterglow', probably launched by a supermassive black hole with spin greater than approximately 0.3. Using four years of Zwicky Transient Facility10 survey data, we calculate a rate of [Formula: see text] per gigapascals cubed per year for on-axis jetted TDEs on the basis of the luminous, fast-fading red component, thus providing a measurement complementary to the rates derived from X-ray and radio observations11. Correcting for the beaming angle effects, this rate confirms that approximately 1 per cent of TDEs have relativistic jets. Optical surveys can use AT2022cmc as a prototype to unveil a population of jetted TDEs.

Catalytic Strategies for the Cycloaddition of CO2 to Epoxides in Aqueous Media to Enhance the Activity and Recyclability of Molecular Organocatalysts.

The cycloaddition of CO2 to epoxides to afford versatile and useful cyclic carbonate compounds is a highly investigated method for the nonreductive upcycling of CO2. One of the main focuses of the current research in this area is the discovery of readily available, sustainable, and inexpensive catalysts, and of catalytic methodologies that allow their seamless solvent-free recycling. Water, often regarded as an undesirable pollutant in the cycloaddition process, is progressively emerging as a helpful reaction component. On the one hand, it serves as an inexpensive hydrogen bond donor (HBD) to enhance the performance of ionic compounds; on the other hand, aqueous media allow the development of diverse catalytic protocols that can boost catalytic performance or ease the recycling of molecular catalysts. An overview of the advances in the use of aqueous and biphasic aqueous systems for the cycloaddition of CO2 to epoxides is provided in this work along with recommendations for possible future developments.

Organocatalytic Polymers from Affordable and Readily Available Building Blocks for the Cycloaddition of CO2 to Epoxides.

The catalytic cycloaddition of CO2 to epoxides to afford cyclic carbonates as useful monomers, intermediates, solvents, and additives is a continuously growing field of investigation as a way to carry out the atom-economic conversion of CO2 to value-added products. Metal-free organocatalytic compounds are attractive systems among various catalysts for such transformations because they are inexpensive, nontoxic, and readily available. Herein, we highlight and discuss key advances in the development of polymer-based organocatalytic materials that match these requirements of affordability and availability by considering their synthetic routes, the monomers, and the supports employed. The discussion is organized according to the number (monofunctional versus bifunctional materials) and type of catalytically active moieties, including both halide-based and halide-free systems. Two general synthetic approaches are identified based on the postsynthetic functionalization of polymeric supports or the copolymerization of monomers bearing catalytically active moieties. After a review of the material syntheses and catalytic activities, the chemical and structural features affecting catalytic performance are discussed. Based on such analysis, some strategies for the future design of affordable and readily available polymer-based organocatalysts with enhanced catalytic activity under mild conditions are considered.

Samarium- and Ytterbium-Grafted Periodic Mesoporous Silica for Carbon Dioxide Capture and Conversion.

Immobilized coordination compounds of Lewis acidic metals are powerful catalytic components of systems for the cycloaddition of CO2 to epoxides that do not require sophisticated coordination frameworks to harness the metal center and modulate its activity. Surface organometallic chemistry (SOMC) is a valuable methodology to prepare well-defined and site-isolated surface complexes and coordination compounds on metal oxides, with ligand environments easily adjustable to a targeted catalytic reaction. In this work, the SOMC methodology is applied to prepare SmII, YbII, and SmIII alkoxide surface complexes on periodic mesoporous (organo)silica of distinct pore symmetry/size for application in the CO2 cycloaddition reaction. The surface complexes are readily accessible by the grafting of the bis(trimethylsilyl)amide precursors LnII[N(SiMe3)2]2(THF)2 (Ln = Sm, Yb) and SmIII[N(SiMe3)2]3, followed by ligand exchange with alcohols (ethanol and neopentanol). The use of periodic mesoporous supports led to hybrid materials with relatively high surface areas and pore sizes, affording good performance in CO2 capture and in the cycloaddition of CO2 to epoxides under mild conditions (60-80 °C, 1-10 bar). In terms of catalytic performance, recyclability, and low amount of added nucleophile TBAX (X = Br, I), the most active materials prepared in this work compare well to a variety of previously reported SOMC-derived surface complexes and to other heterogeneous Lewis acids displaying more elaborate ligand environments.

Enhancing the Catalytic Performance of Group I, II Metal Halides in the Cycloaddition of CO2 to Epoxides under Atmospheric Conditions by Cooperation with Homogeneous and Heterogeneous Highly Nucleophilic Aminopyridines: Experimental and Theoretical Study.

Compared to metal-organic complexes and transition-metal halides, group I metal halides are attractive catalysts for the crucial cycloaddition reaction of CO2 to epoxides as they are ubiquitously available and inexpensive, have a low molecular weight, and are not based on (potentially) endangered metals, especially for the case of sodium and potassium. Nevertheless, given their low intrinsic catalytic efficiency, they require the assistance of additional catalytic moieties. In this work, we show that by exploiting the high nucleophilicity of opportunely designed aminopyridines, catalytic systems based on alkaline metals can be formed, which allow the cycloaddition of CO2 to epoxides to proceed under atmospheric pressure at moderate temperatures. Importantly, the aminopyridine nucleophiles can be applied in their heterogenized form, leading to a recyclable catalytic system. An investigation of the reaction mechanism by density functional theory calculations shows that metal halide complexes and nucleophilic pyridines can work as a dual cooperative catalytic system where the use of aminopyridines leads to lower energy barriers for the opening of the epoxide ring, and halide-adducts are involved in the subsequent steps of CO2 insertion and ring closure.

The Comparison between Single Atom Catalysis and Surface Organometallic Catalysis.

Single atom catalysis (SAC) is a recent discipline of heterogeneous catalysis for which a single atom on a surface is able to carry out various catalytic reactions. A kind of revolution in heterogeneous catalysis by metals for which it was assumed that specific sites or defects of a nanoparticle were necessary to activate substrates in catalytic reactions. In another extreme of the spectrum, surface organometallic chemistry (SOMC), and, by extension, surface organometallic catalysis (SOMCat), have demonstrated that single atoms on a surface, but this time with specific ligands, could lead to a more predictive approach in heterogeneous catalysis. The predictive character of SOMCat was just the result of intuitive mechanisms derived from the elementary steps of molecular chemistry. This review article will compare the aspects of single atom catalysis and surface organometallic catalysis by considering several specific catalytic reactions, some of which exist for both fields, whereas others might see mutual overlap in the future. After a definition of both domains, a detailed approach of the methods, mostly modeling and spectroscopy, will be followed by a detailed analysis of catalytic reactions: hydrogenation, dehydrogenation, hydrogenolysis, oxidative dehydrogenation, alkane and cycloalkane metathesis, methane activation, metathetic oxidation, CO2 activation to cyclic carbonates, imine metathesis, and selective catalytic reduction (SCR) reactions. A prospective resulting from present knowledge is showing the emergence of a new discipline from the overlap between the two areas.

Surface organometallic chemistry in heterogeneous catalysis.

The broad challenges of energy and environment have become a main focus of research efforts to develop more active and selective catalytic systems for key chemical transformations. Surface organometallic chemistry (SOMC) is an established concept, associated with specific tools, for the design, preparation and characterization of well-defined single-site catalysts. The objective is to enter a catalytic cycle through a presumed catalytic intermediate prepared from organometallic or coordination compounds to generate well defined surface organometallic fragments (SOMFs) or surface coordination fragments (SCFs). These notions are the basis of the "catalysis by design" strategy ("structure-activity" relationship) in which a better understanding of the mechanistic aspects of the catalytic process led to the improvement of catalyst performances. In this review the application of SOMC strategy for the design and preparation of catalysts for industrially relevant processes that are crucial to the energy and environment is discussed. In particular, the focus will be on the conversion of energy-related feedstocks, such as methane and higher alkanes that are primary products of the oil and gas industry, and of their product of combustion, CO2, whose efficient capture and conversion is currently indicated as a top priority for the environment. Among the main topics related to energy and environment, catalytic oxidation is also considered as a key subject of this review.

Physico-chemical investigation of ZnS thin-film deposited from ligand-free nanocrystals synthesized by non-hydrolytic thio-sol-gel.

Ultra-small and monodispersed zinc sulfide nanocrystals (NCs) (d ≤ 3 nm) have been prepared without the use of any surfactants by a synthetic route using benzyl mercaptan as a source of sulfur. The prepared NCs are dispersible in highly polar solvents and display the capability to closely pack-up in a bulky film. The NCs were characterized by TEM, XRD and UV-vis optical absorption as well as by steady-state and time-resolved photoluminescence (PL) spectroscopies. Uniform films of ZnS were spin-coated on glass and ITO-glass substrates using a NCs dispersion in N,N-dimethylformamide. The NCs and the resulting films were characterized by morphological and optoelectronic probing techniques such as AFM, SEM, diffuse reflectance, PL and photoelectron spectroscopy in air. These physical investigations confirmed that the chalcogenide NCs grown by this method have the potential to be utilized directly as photocatalysts and are potentially useful building-blocks/starting materials for the fabrication of semiconductor thin films for optoelectronic applications such as LED, luminescent screens, field effect transistor and solar cells. Insights on the chemistry involved in the NCs growth have been provided revealing that their formation proceeds through a mechanism involving a thioether elimination reaction.

SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions.

Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4) (ImDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImDippNW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-ImDippN] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

Cooperative Effect of Monopodal Silica-Supported Niobium Complex Pairs Enhancing Catalytic Cyclic Carbonate Production.

Recent discoveries highlighted the activity and the intriguing mechanistic features of NbCl5 as a molecular catalyst for the cycloaddition of CO2 and epoxides under ambient conditions. This has inspired the preparation of novel silica-supported Nb species by reacting a molecular niobium precursor, [NbCl5·OEt2], with silica dehydroxylated at 700 °C (SiO(2-700)) or at 200 °C (SiO(2-200)) to generate diverse surface complexes. The product of the reaction between SiO(2-700) and [NbCl5·OEt2] was identified as a monopodal supported surface species, [≡SiONbCl4·OEt2] (1a). The reactions of SiO(2-200) with the niobium precursor, according to two different protocols, generated surface complexes 2a and 3a, presenting significant, but different, populations of the monopodal surface complex along with bipodal [(≡SiO)2NbCl3·OEt2]. (93)Nb solid-state NMR spectra of 1a-3a and (31)P solid-state NMR on their PMe3 derivatives 1b-3b led to the unambiguous assignment of 1a as a single-site monopodal Nb species, while 2a and 3a were found to present two distinct surface-supported components, with 2a being mostly monopodal [≡SiONbCl4·OEt2] and 3a being mostly bipodal [(≡SiO)2NbCl3·OEt2]. A double-quantum/single-quantum (31)P NMR correlation experiment carried out on 2b supported the existence of vicinal Nb centers on the silica surface for this species. 1a-3a were active heterogeneous catalysts for the synthesis of propylene carbonate from CO2 and propylene oxide under mild catalytic conditions; the performance of 2a was found to significantly surpass that of 1a and 3a. With the support of a systematic DFT study carried out on model silica surfaces, the observed differences in catalytic efficiency were correlated with an unprecedented cooperative effect between two neighboring Nb centers on the surface of 2a. This is in an excellent agreement with our previous discoveries regarding the mechanism of NbCl5-catalyzed cycloaddition in the homogeneous phase.

Dynamics of the NbCl5-catalyzed cycloaddition of propylene oxide and CO2 : assessing the dual role of the nucleophilic Co-catalysts.

A mechanistic study on the synthesis of propylene carbonate (PC) from CO2 and propylene oxide (PO) catalyzed by NbCl5 and organic nucleophiles such as 4-dimethylaminopyridine (DMAP) or tetra-n-butylammonium bromide (NBu4 Br) is reported. A combination of in situ spectroscopic techniques and kinetic studies has been used to provide detailed insight into the reaction mechanism, the formation of intermediates, and interactions between the reaction partners. The results of DFT calculations support the experimental observations and allow us to propose a mechanism for this reaction.

Revisiting the Potential of Group VI Inorganic Precatalysts for the Ethenolysis of Fatty Acids through a Mechanochemical Approach.

The utilization of biobased feedstocks to prepare useful compounds is a pivotal trend in current chemical research. Among a varied portfolio of naturally available starting materials, fatty acids are abundant, versatile substrates with multiple applications. In this context, the ethenolysis of unsaturated fatty acid esters such as methyl oleate is an atom-economical way to prepare functional C10 olefins with a biobased footprint. Despite the existence of a variety of metathesis catalysts for the latter process, there is a lack of readily available, efficient, and inexpensive catalytic systems based on earth-abundant metals (Mo, W) whose preparation does not require sophisticated syntheses and manipulations. Here, a systematic exploration of homogeneous and heterogeneous inorganic Mo, W (oxy)halides shows that MoOCl4, while inactive as a homogeneous species, forms active and selective silica-supported ethenolysis precatalysts able to reach equilibrium conversion of methyl oleate within a few minutes upon activation with SnMe4. Such heterogeneous MoOCl4-based precatalysts were easily accessed through mechanochemical solvent-free procedures and found to contain, upon characterization by elemental analysis and Raman spectroscopy, isolated (≡SiO)Mo(=O)Cl3 units or polymeric silica-supported [-O(≡SiO)nMoCl4-nO-]m (n = 1, 2) complexes depending on the molybdenum loading. The former isolated species exhibited a higher catalytic performance. The developed heterogeneous precatalysts could be applied to the ethenolysis of various substrates, including polyunsaturated fatty acid esters and industrial fatty acid methyl ester (FAME) mixtures from palm oil transesterification.

Catalysts Prepared from Atomically Dispersed Ce(III) on MgO Rival Bulk Ceria for CO Oxidation.

Atomically dispersed cerium catalysts on an inert, crystalline MgO powder support were prepared by using both Ce(III) and Ce(IV) precursors. The materials were used as catalysts for CO oxidation in a once-through flow reactor and characterized by atomic-resolution scanning transmission electron microscopy, X-ray absorption near-edge structure spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed reduction, among other techniques, before and after catalysis. The most active catalysts, formed from the precursor incorporating Ce(III), displayed performance similar to that reported for bulk ceria under comparable conditions. The catalyst provided stable time-on-stream performance for as long as it was kept on-stream, 2 days, increasing slightly in activity as the atomically dispersed cerium ions were transformed into ceria nanodomains represented as CeOx and having increased reducibility on the MgO support. The results suggest how highly dispersed supported ceria catalysts with low cerium loadings can be prepared and may pave the way for improved efficiencies of cerium utilization in oxidation catalysis.

Hydrophobically-enhanced "on water" cycloaddition of CO2 to long-chain terminal epoxides.

Long-chain cyclic carbonates (LC-CC) are attractive building blocks and non-ionic surfactants. We demonstrate a convenient methodology to prepare LC-CC in miniemulsions of epoxide droplets in water. The pre-organization and confinement of the reagents from H-bond and hydrophobic interactions allow the target process to proceed at mild temperatures under atmospheric CO2.

Simple Halogen-Free, Biobased Organic Salts Convert Glycidol to Glycerol Carbonate under Atmospheric CO2 Pressure.

Glycerol carbonate (GC) has emerged as an attractive synthetic target due to various promising technological applications. Among several viable strategies to produce GC from CO2 and glycerol and its derivatives, the cycloaddition of CO2 to glycidol represents an atom-economic an efficient strategy that can proceed via a halide-free manifold through a proton-shuttling mechanism. Here, it was shown that the synthesis of GC can be promoted by bio-based and readily available organic salts leading to quantitative GC formation under atmospheric CO2 pressure and moderate temperatures. Comparative and mechanistic experiments using sodium citrate as the most efficient catalyst highlighted the role of both hydrogen bond donor and weakly basic sites in the organic salt towards GC formation. The citrate salt was also used as a catalyst for the conversion of other epoxy alcohols. Importantly, the discovery that homogeneous organic salts catalyze the target reaction inspired us to use metal alginates as heterogeneous and recoverable bio-based catalysts for the same process.

Microwave-Assisted Non-aqueous and Low-Temperature Synthesis of Titania and Niobium-Doped Titania Nanocrystals and Their Application in Halide Perovskite Solar Cells as Electron Transport Layers.

Undoped and Nb-doped TiO2 nanocrystals are prepared by a microwave-assisted non-aqueous sol-gel method based on a slow alkyl chloride elimination reaction between metal chlorides and benzyl alcohol. Sub-4 nm nanoparticles are grown under microwave irradiation at 80 °C in only 3 h with precise control of growth parameters and yield. The obtained nanocrystals could be conveniently used to cast compact TiO2 or Nb-doped TiO2 electron transport layers for application in formamidinium lead iodide-based photovoltaic devices. Niobium doping is found to improve the cell performance by increasing the conductivity and mobility of the electron transport layer. At the same time, a measurable decrease in parasitic light absorption in the low wavelength portion of the spectrum was observed.

Dataset for the synthesis and application of single-component heterogeneous catalysts based on zinc and tin for the cycloaddition of pure, diluted, and impure CO2 to epoxides under mild conditions.

The cycloaddition of CO2 to epoxides under mild conditions is a growing field of research and a viable strategy to recycle CO2 in the form of cyclic carbonates as useful intermediates, solvents, and additives. This target requires readily accessible and recyclable catalysts whose synthesis does not involve expensive monomers, multistep procedures, coupling reagents, etc. Additionally, the catalysts should be active under atmospheric pressure and tolerate impurities such as methane and H2S. In a recent manuscript (Rational engineering of single-component heterogeneous catalysts based on abundant metal centers for the mild conversion of pure and impure CO2 to cyclic carbonates; Chemical Engineering Journal 422 (2021) 129930) we have developed strategies to prepare efficient heterogeneous catalysts for the cycloaddition reaction of CO2 to epoxides. Such materials consist of dispersions of metal halides (ZnCl2 or SnCl4) on silica support that is further functionalized with ionic liquids bearing nucleophilic halide moieties for cooperative epoxide activation and ring-opening. Herein, we provide useful complementary data for the characterization of the prepared materials in the form of: SEM images of materials (SEM: scanning electron microscope), SEM-EDS images of materials (EDS: Energy-dispersive X-ray spectroscopy), TEM images of materials (TEM: transmission electron microscope); XPS (X-ray photoelectron spectroscopy) survey spectra of most active catalysts and related high-resolution spectra in spectral regions of interest, BET (Brunauer-Emmett-Teller) physisorption isotherms of materials, raw 1H NMR spectra of catalytic reactions to verify the reproducibility of the reaction outcome and identify the reaction products.

Residual dipolar couplings in short peptidic foldamers: combined analyses of backbone and side-chain conformations and evaluation of structure coordinates of rigid unnatural amino acids.

A flexible tool for rigid systems. Residual dipolar couplings (RDCs) have proven to be valuable NMR structural parameters that provide insights into the backbone conformations of short linear peptidic foldamers, as illustrated here. This study demonstrates that RDCs at natural abundance can provide essential structural information even in the case of short linear peptides with unnatural amino acids. In addition, they allow for the detection of proline side-chain conformations and are used as a quality check for the parameterizations of rigid unnatural amino acids.

Polymers Based on Cyclic Carbonates as Trait d'Union Between Polymer Chemistry and Sustainable CO2 Utilization.

Given the large amount of anthropogenic CO2 emissions, it is advantageous to use CO2 as feedstock for the fabrication of everyday products, such as fuels and materials. An attractive way to use CO2 in the synthesis of polymers is by the formation of five-membered cyclic organic carbonate monomers (5CCs). The sustainability of this synthetic approach is increased by using scaffolds prepared from renewable resources. Indeed, recent years have seen the rise of various types of carbonate syntheses and applications. 5CC monomers are often polymerized with diamines to yield polyhydroxyurethanes (PHU). Foams are developed from this type of polymers; moreover, the additional hydroxyl groups in PHU, absent in classical polyurethanes, lead to coatings with excellent adhesive properties. Furthermore, carbonate groups in polymers offer the possibility of post-functionalization, such as curing reactions under mild conditions. Finally, the polarity of carbonate groups is remarkably high, so polymers with carbonates side-chains can be used as polymer electrolytes in batteries or as conductive membranes. The target of this Review is to highlight the multiple opportunities offered by polymers prepared from and/or containing 5CCs. Firstly, the preparation of several classes of 5CCs is discussed with special focus on the sustainability of the synthetic routes. Thereafter, specific classes of polymers are discussed for which the use and/or presence of carbonate moieties is crucial to impart the targeted properties (foams, adhesives, polymers for energy applications, and other functional materials).