Efficient Electrochemical Reduction of CO2 to Formate in Methanol Solutions by Mn Functionalized Electrodes in the Presence of Amines

Carbon cloth electrode modified by covalently attaching a manganese organometallic catalyst is used as cathode for the electrochemical recuction of CO2 in methanol solutions. Six different amines are employed as co-catalyst in millimolar concentrations, which coupled to the increased solubility of CO2 in methanol enhance the formate production, switch the selectivity toward formate anion, and in the case of pentamethyldiethylentriamine (PMDETA) resulted in an impressive TONHCOO– of 2.8×104. We demonstrate that the protonated PMDETA is formed in methanol solution by simply bubbling CO2, which is the responsible for a barrierless transformation of CO2 to formate via the reduced form of the Mn catalyst covalently bonded to the electrode surface. These findings pave the way for more efficient transformation of CO2 into liquid fuel and shed light on the electrochemical mechanism

Pd Doped on TCH@SBA-15 Nanocomposites: Fabrication and Application as a New Organometallic Catalyst in the Three-Component Synthesis of N-Benzo-imidazo- or -thiazole-1,3-thiazolidinones

In this study, Pd(II)/TCH@SBA-15 nanocomposites were synthesized by the grafting of 3-chloropropyltriethoxysilane and thiocarbohydrazide on SBA-15 and subsequent deposition of palladium acetates through the ligand–metal coordination method. The structure and morphology of this nanoporous nanocomposite was thoroughly identified by Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, thermogravimetric analysis, atomic absorption spectroscopy, and Brunauer–Emmett–Teller instrumental analyses. Furthermore, the catalytic activity of this nanocomposite was investigated in the three-component synthesis of 3-benzimidazolyl or benzothiazoleyl-1,3-thiazolidin-4-ones via a reaction of 2-aminobenzimidazole or 2-aminobenzothiazole, aromatic aldehydes, and thioglycolic acid in an acetone–H2O mixture under green conditions. The Pd/TCH@SBA-15 nanocatalyst is demonstrated to exhibit a high catalyzing activity in the three-component reaction of the synthesis of N-heterocyclic thiazolidinones with good to excellent yields. One of the advantages of the suggested method is the direct application of the thiocarbohydrazide ligand to stabilize Pd nanoparticles through formation of a stable ring complex without creating an additional Schiff base step. Moreover, this organometallic nanocatalyst can be recycled several times with no notable leaching or loss of performance.

Effect of New Eco-Polyols Based on PLA Waste on the Basic Properties of Rigid Polyurethane and Polyurethane/Polyisocyanurate Foams

The aim of the presented research was to obtain two new eco-polyols based on waste polylactide (PLA) and to check the effect on the properties of rigid polyurethane (RPU) foams and, based on these, rigid polyurethane/polyisocyanurate (RPU/PIR) foams. The synthesis of eco-polyols was based on the transesterification reaction of melted PLA with diethylene glycol in the presence of an organometallic catalyst. Properties of the obtained eco-polyols were examined for their potential as raw materials for synthesis of rigid polyurethane and polyisocyanurate foams, i.e., hydroxyl value, acid value, density, viscosity, pH, water content. Spectroscopic studies (FTIR, 1H NMR and 13C NMR) were also carried out. Results of these tests confirmed the assumed chemical structure of the new polyols. RPU and RPU/PIR foam formulations were developed based on the obtained analytical results. Partial replacement of petrochemical polyol by eco-polyols in RPU and RPU/PIR foams decreased the value of apparent density, compressive strength, brittleness and water absorption. Moreover, all foams modified by eco-polyols showed higher resistance to aging. All RPU/PIR foams and most PRU foams modified by eco-polyols from waste PLA had better functional properties than the reference foams based on petrochemical polyol.

Double Crystallization and Phase Separation in Polyethylene—Syndiotactic Polypropylene Di-Block Copolymers

Crystallization and phase separation in the melt in semicrystalline block copolymers (BCPs) compete in defining the final solid state structure and morphology. In crystalline–crystalline di-block copolymers the sequence of crystallization of the two blocks plays a definitive role. In this work we show that the use of epitaxial crystallization on selected crystalline substrates allows achieving of a control over the crystallization of the blocks by inducing crystal orientations of the different crystalline phases and a final control over the global morphology. A sample of polyethylene-block-syndiotactic polypropylene (PE-b-sPP) block copolymers has been synthesized with a stereoselective living organometallic catalyst and epitaxially crystallized onto crystals of two different crystalline substrates, p-terphenyl (3Ph) and benzoic acid (BA). The epitaxial crystallization on both substrates produces formation of highly ordered morphologies with crystalline lamellae of sPP and PE highly oriented along one direction. However, the epitaxial crystallization onto 3Ph should generate a single orientation of sPP crystalline lamellae highly aligned along one direction and a double orientation of PE lamellae, whereas BA crystals should induce high orientation of only PE crystalline lamellae. Thanks to the use of the two selective substrates, the final morphology reveals the sequence of crystallization events during cooling from the melt and what is the dominant event that drives the final morphology. The observed single orientation of both crystalline PE and sPP phases on both substrates, indeed, indicates that sPP crystallizes first onto 3Ph defining the overall morphology and PE crystallizes after sPP in the confined interlamellar sPP regions. Instead, PE crystallizes first onto BA defining the overall morphology and sPP crystallizes after PE in the confined interlamellar PE regions. This allows for discriminating between the different crystalline phases and defining the final morphology, which depends on which polymer block crystallizes first on the substrate. This work also shows that the use of epitaxial crystallization and the choice of suitable substrate offer a means to produce oriented nanostructures and morphologies of block copolymers depending on the composition and the substrates.

Advances in heterometallic ring-opening (co)polymerisation catalysis

Truly sustainable plastics require renewable feedstocks coupled with efficient production and end-of-life degradation/recycling processes. Some of the most useful degradable materials are aliphatic polyesters, polycarbonates and polyamides, which are often prepared via ring-opening (co)polymerisation (RO(CO)P) using an organometallic catalyst. While there has been extensive research into ligand development, heterometallic cooperativity offers an equally promising yet underexplored strategy to improve catalyst performance, as heterometallic catalysts often exhibit significant activity and selectivity enhancements compared to their homometallic counterparts. This review describes advances in heterometallic RO(CO)P catalyst design, highlighting the overarching structure-activity trends and reactivity patterns to inform future catalyst design.

Site-Selective Palladium-Catalyzed Oxidation of Glucose in Glycopeptides

<p>Here we report a novel method of site-selective oxidation of glucose moieties on individual glycopeptides and on a mixture of tryptic glycopeptides. The organometallic catalyst [(neocuproine)PdOAc]₂OTf₂, that was previously shown to perform regioselective C3-oxidation of glucosides, was used in the scope of this work. The selectivity of the catalyst towards glucose and the sensitivity of specific amino acid residues to oxidation was explored by screening a select panel of glycopeptides in the oxidation reactions. We reveal that glucosylated peptides are more readily oxidized compared to galactosylated peptides, and Thr/Ser-oxidation is a concomitant side-reaction. The oxidation methodology was also applied to the complex mixture of tryptic glucopeptides that was generated from the fragment of <i>Haemophilus influenzae</i> adhesin glycoprotein. The resulting keto-group of the glucose was further transformed into an oxime functionality, which allows introduction of various groups of interest. The methodology outlined in this work will allow to perfrom late-stage modification of glucopeptides as well as selective oxidation and functionalization of tryptic glucopeptides for proteomics analysis. </p>

Site-Selective Palladium-Catalyzed Oxidation of Glucose in Glycopeptides

<p>Here we report a novel method of site-selective oxidation of glucose moieties on individual glycopeptides and on a mixture of tryptic glycopeptides. The organometallic catalyst [(neocuproine)PdOAc]₂OTf₂, that was previously shown to perform regioselective C3-oxidation of glucosides, was used in the scope of this work. The selectivity of the catalyst towards glucose and the sensitivity of specific amino acid residues to oxidation was explored by screening a select panel of glycopeptides in the oxidation reactions. We reveal that glucosylated peptides are more readily oxidized compared to galactosylated peptides, and Thr/Ser-oxidation is a concomitant side-reaction. The oxidation methodology was also applied to the complex mixture of tryptic glucopeptides that was generated from the fragment of <i>Haemophilus influenzae</i> adhesin glycoprotein. The resulting keto-group of the glucose was further transformed into an oxime functionality, which allows introduction of various groups of interest. The methodology outlined in this work will allow to perfrom late-stage modification of glucopeptides as well as selective oxidation and functionalization of tryptic glucopeptides for proteomics analysis. </p>