Photoreduction of carbon dioxide to carbon monoxide with hydrogen catalyzed by a rhenium(i) phenanthroline-polyoxometalate hybrid complex

A phenanthroline ligand decorated at the 5,6-position with a 15-crown-5 ether was used to prepare a metalorganic-polyoxometalate hybrid complex Re(I)(L)(CO)(3)CH(3)CN-MHPW(12)O(40) (L = 15-crown-5-phenanthroline, M = Na(+), H(3)O(+)). X-ray diffraction, (1)H and (13)C NMR, ESI-MS, IR, and elemental analysis were used to characterize this complex. In the presence of Pt/C, the polyoxometalate moiety in Re(I)(L)(CO)(3)CH(3)CN-MHPW(12)O(40) can oxidize H(2) to two protons and two electrons which in the presence of visible light can catalyze the photoreduction of CO(2) to CO with H(2) as the reducing agent instead of the universally used amines as sacrificial reducing agents. An EPR spectrum of a stable intermediate species under reaction conditions shows characteristics of a PW(V)W(VI)(11)O(40) and a Re(0) species with a tentative assignment of the intermediate as Re(0)(L)(CO)(3)(S)-MH(3)PW(V)W(VI)(11)O(40).     

Sol–Gel Entrapped Lewis Acids as Catalysts for Biodiesel Production

Replacing fossil fuels with biodiesel enables the emission of greenhouse gases to be decreased and reduces dependence on fossil fuels in countries with poor natural resources. Biodiesel can be produced by an esterification reaction between free fatty acids (FFAs) and methanol or by transesterification of triglycerides from oils. Both reactions require homogeneous or heterogeneous catalysis. Production of biodiesel catalyzed by heterogeneous catalysts seems to be the preferred route, enabling easy product separation. As we have previously shown, the Lewis acids AlCl₃ and BF₃ can serve as highly efficient catalysts under ultrasonic activation. The present study focused on the development of oleic acid (OA) esterification with methanol by the same catalysts immobilized in silica matrices using the sol–gel synthesis route. During the course of immobilization, AlCl₃ converts to AlCl₃ × 6H₂O (aluminite) and BF₃ is hydrolyzed with the production of B₂O₃. The immobilized catalysts can be reused or involved in a continuous process. The possibility of biodiesel production using immobilized catalysts under ultrasonic activation is shown for the conversion of FFAs into biodiesel in batch and continuous mode.     

Catalytic Stereoselective Borylative Transannular Reactions

Medium‐sized carbocycles containing an α,β‐unsaturated ketone moiety as Michael acceptor site and a ketone moiety as internal electrophilic site are ideal substrates to conduct Cu(I)‐catalyzed conjugated borylation followed by electrophilic intramolecular trapping that results into a pioneer transannular borylative ring closing reaction. The relative configuration of three adjacent stereocenters is controlled, giving access to a single diastereoisomer for a wide range of substrates tested. Moreover, when a chiral ligand is incorporated, the reaction provides enantioenriched polycyclic products with up to 99 % ee.     

The Mechanical Role of Metal Ions in Biogenic Protein‐Based Materials

Protein‐metal interactions—traditionally regarded for roles in metabolic processes—are now known to enhance the performance of certain biogenic materials, influencing properties such as hardness, toughness, adhesion, and self‐healing. Design principles elucidated through thorough study of such materials are yielding vital insights for the design of biomimetic metallopolymers with industrial and biomedical applications. Recent advances in the understanding of the biological structure–function relationships are highlighted here with a specific focus on materials such as arthropod biting parts, mussel byssal threads, and sandcastle worm cement.     

Templating nanostructures by mesoporous materials with an emphasis on room temperature and cryogenic TEM studies

Rapid strides realized in the field of ordered mesoporous silica (OMS) with a well-defined pore shape and nanometric sizes, provide new gateways for the preparation of nanostructured materials having controlled shape and size with a very narrow distribution. The focus of the current review is on the synthesis of nanostructures templated by OMS either in bulk or in thin film form. The importance of electron microscopy as an indispensable technique in the structural characterization of OMS templated nanostructures, including cryo-TEM, electron tomography and HR-SEM, is highlighted in this review.     

Synthesis, structure, and reactivity of rhodium and iridium complexes of the chelating bis-sulfoxide tBuSOC2H4SOtBu. Selective O-H activation of 2-hydroxy-isopropyl-pyridine

The chloro-bridged rhodium and iridium complexes [M2(BTSE)2Cl2] (M = Rh 1, Ir 2) bearing the chelating bis-sulfoxide tBuSOC2H4SOtBu (BTSE) were prepared by the reaction of [M2(COE)4Cl2] (M = Rh, Ir; COE = cyclooctene) with an excess of a racemic mixture of the ligand. The cationic compounds [M(BTSE)2][PF6] (M = Rh 3, Ir 4), bearing one S- and one O-bonded sulfoxide, were also obtained in good yields. The chloro-bridges in 2 can be cleaved with 2-methyl-6-pyridinemethanol and 2-aminomethyl pyridine, resulting in the iridium(I) complexes [Ir(BTSE)(Py)(Cl)] (Py = 2-methyl-6-pyridinemethanol 5, 2-aminomethyl-pyridine 6). In case of the bulky 2-hydroxy- isopropyl-pyridine, selective OH oxidative addition took place, forming the Ir(III)-hydride [Ir(BTSE)(2-isopropoxy-pyridine)(H)(Cl)] 7, with no competition from the six properly oriented C-H bonds. The cationic rhodium(I) and iridium(I) compounds [M(BTSE)(2-aminomethyl-pyridine)][X] (M = Rh 8, Ir 10), [Rh(BTSE)(2-hydroxy- isopropyl-pyridine)][X] 9(stabilized by intramolecular hydrogen bonding), [Ir(BTSE)(pyridine)2][PF6] 12, [Ir(BTSE)(alpha-picoline)2][PF6] 13, and [Rh(BTSE)(1,10-phenanthroline)][PF6] 14 were prepared either by chloride abstraction from the dimeric precursors or by replacement of the labile oxygen bonded sulfoxide in 3 or 4. Complex 14 exhibits a dimeric structure in the solid state by pi-pi stacking of the phenanthroline ligands.     

Effect of pore size on adsorption of a polyelectrolyte to porous glass

The adsorption of quaternized poly(vinylpyridine) (QPVP) on controlled pore glass (CPG) size, over the ionic strength range 0.001-0.5 M was found to display nonmonotonic behavior as a function of pore size. Both adsorption kinetics and ionic strength effects deviated dramatically from behavior typical of adsorption on flat surfaces when the ratio of the pore radius Rp to the polymer hydrodynamic radius Rh became smaller than ca. 2. Ionic strength enhancement of adsorption for small pore sizes was observed at much higher salt concentrations than is typical for polycation adsorption on flat surfaces. The amount of polymer adsorbed per unit surface area of glass GammaA, in 0.5 M NaCl, exhibited a shallow maximum at Rp/Rh approximately 5. Since the value of GammaA for small pore size CPG is strongly depressed by the large surface area, an alternative and more interesting observation is that the amount of polymer adsorbed per gram of CPG, Gammaw, displays a strong maximum when Rp is equal to or slightly smaller than Rh. The efficiency with which QPVP binds anionic micelles to (negatively charged) CPG (grams of surfactant/grams of QPVP) increases strongly with diminishing pore size, indicating that the configuration of polycation bound to small pores favors micelle binding. Since the micelles are larger than small pores, the results indicate that when Rp < Rh, adsorbed polycation molecules reside only partially within the pore. The results of this study are supported by simulations of polyelectrolytes within cylindrical cavities.     

Growth of Au/Ag nanowires in thin surfactant solution films: an electron microscopy study

The surfactant templated gold-silver nanowire growth process in a thin solution film was probed by cryo-transmission electron microscopy (cryo-TEM). The increasing surfactant concentration upon film drying appears to induce phase transformations in the film and form a liquid crystalline template for the nanowires growth. High-resolution transmission electron microscopy (HRTEM) and electron holography revealed that the nanowires were polycrystalline with some preferred crystallite orientations and had a roughly cylindrical cross-section. Further improvement of the technique may lead to highly ordered metal nanowire arrays within the surfactant matrix similar to the closely related mesoporous materials.     

Assessment of PHB with varying hydroxyvalerate content for potential packaging applications

Poly-(hydroxybutyrate) (PHB) is biodegradable aliphatic polyester that is produced by a wide range of microorganisms. Basic PHB has relatively high glass transition and melting temperatures. To improve flexibility for potential packaging applications, PHB is synthesized with various co-polymers such as poly-(3-hydroxyvalerate) (HV) leading to a decrease of the glass transitions and melting temperatures. In addition, the HV broadens the processing window since there is improved melt stability at lower processing temperatures. In this study, PHB synthesized with different valerate contents (5%, 12%, and 20%) and varying in molecular weights were characterized. All PHBV materials displayed a glass transition between −10 and 20 °C. The two melting transitions found for Aldrich 5%, 12%, and Tianan 20%, resulted from crystals formed during cooling of the samples. The complex viscosity decreased with increasing temperature due to a decrease in molecular weights of the samples. These results suggest that processing the co-polymer below 160 °C would be beneficial with low screw speed. The mechanical results indicate all PHBV materials had high elastic modulus and flexural strength with low tensile strength and elongation at break. The WVTR results indicated the polymer to be very hydrophilic, resulting in higher water transmission rates.