Plasmonic heating using an easily recyclable Pd-functionalized Fe3O4/Au core-shell nanoparticle catalyst for the Suzuki and Sonogashira reaction

Palladium functionalized gold nanoparticles were used in the past as a catalyst system in light induced cross-coupling reactions, but with a main limitation of the recuperation. To overcome this problem, a palladium functionalized Fe₃O₄/Au core-shell nanoparticle was successfully synthesized with a peak wavelength of 680 nm from the plasmon resonance of the gold shell. By the presence of the magnetite core, the nanoparticle catalyst can easily be removed using magnetic precipitation. This is accompanied with the advantage of having less valuable gold present in the system. The gold shell makes it possible to induce local heating using plasmon resonance. By this combination, it is possible to recuperate the catalyst system using magnetic precipitation and increase the control and safety of the reaction due to the presence of the light-induced plasmonic heating. It was possible to perform light-induced Suzuki cross-coupling reactions using this catalyst system, but with a dependency of the substrate. It was found that an anionic substrate is repulsed from the negatively charged core-shell nanoparticle. The catalyst was examined on its recuperation abilities and could be reused up to 5 cycles. At the catalytic site a temperature was reached between 40 °C and 45 °C. Despite the promising results of the Suzuki reaction, it was not possible to perform light-induced Sonogashira reactions due to the insufficient heat generation at the catalytic site. Nevertheless, these results are promising in the development of an easily recyclable catalyst together with an alternative heating source, resulting in an increase of control and safety.     

Site‐Selective,Modular Diversification of Polyhalogenated Aryl Fluorosulfates (ArOSO2F) Enabled by an Air‐Stable PdI Dimer

Since 2014, the interest in aryl fluorosulfates (ArOSO₂F) as well as their implementation in powerful applications has continuously grown. In this context, the enabling capability of ArOSO₂F will strongly depend on the substitution pattern of the arene, which ultimately dictates its overall function as drug candidate, material, or bio‐linker. This report showcases the modular, substrate‐independent, and fully predictable, selective functionalization of polysubstituted arenes bearing C?OSO₂F, C?Br, and C?Cl sites, which makes it possible to diversify the arene in the presence of OSO₂F or utilize OSO₂F as a triflate surrogate. Sequential and triply selective arylations and alkylations were realized within minutes at room temperature, using a single and air‐stable Pd^I dimer.     

Determination of 7-Dimensional Indecomposable Nilpotent Complex Lie Algebras by Adjoining a Derivation to 6-Dimensional Lie Algebras

For any complex 6-dimensional nilpotent Lie algebra \mathfrakg,\mathfrak{g}, we compute the strain of all indecomposable 7-dimensional nilpotent Lie algebras which contain \mathfrakg\mathfrak{g} by the adjoining a derivation method. We get a new determination of all 7-dimensional complex nilpotent Lie algebras, allowing to check earlier results (some contain errors), along with a cross table intertwining nilpotent 6- and 7-dimensional Lie algebras.     

Palladium-catalyzed microwave-assisted amination of 1-bromonaphthalenes and 5- and 8-bromoquinolines

[reaction: see text] 1-Aminonaphthalenes and 5- and 8-aminoquinolines were rapidly prepared from the respective aryl bromides in good yields by Pd-catalyzed aryl amination under microwave conditions. Consistent improvements in yields over those obtained under standard conditions were seen with quinoline substrates. In the cases where 5-bromo-8-cyanoquinoline was used as a substrate, no desired products were obtained under standard conditions with a number of different primary and secondary amines. However, microwave conditions provided the desired products in good to excellent yields.     

Rheometric properties of micron-sized CaCO3 suspensions stabilised by a physical polyol/silica gel for polyurethane foams

This article considers the rheometric properties of mixtures containing a micron-sized mineral filler of calcium carbonate (CaCO₃) in a polymer matrix gelled by adding colloidal silica (CS). These mixtures, consisting of a polymer matrix (polyols, catalysts, surfactant) are used to produce polyurethane foams. The suspending phase (polymer matrix/CS) has a yield stress that has been linked to fractal aggregation of the colloidal filler. Suspensions without any colloidal silica (polymer matrix/CaCO₃), show aggregation of CaCO₃ which is most probably due to the adsorption of catalysts present in the polymer matrix. Beyond a critical CaCO₃ volume fraction, a yield stress is detected indicating a 3D connected structure. In the case of suspensions containing colloidal silica (polymer matrix/CaCO₃/SC), the yield stress is due to a combination of the fractal network formed by the colloidal silica and aggregation of the micron-sized particles of CaCO₃.     

Rapid Room‐Temperature,Chemoselective C −C Coupling of Poly(pseudo)halogenated Arenes Enabled by Palladium(I) Catalysis in Air

While chemoselectivities in Pd⁰‐catalyzed coupling reactions are frequently non‐intuitive and a result of a complex interplay of ligand/catalyst, substrate, and reaction conditions, we herein report a general method based on Pd^I that allows for an a priori predictable chemoselective C −C coupling at C−Br in preference to C−OTf and C−Cl bonds, regardless of the electronic or steric bias of the substrate. The C−C bond formations are extremely rapid (<5 min at RT) and are catalyzed by an air‐ and moisture‐stable Pd^I dimer under open‐flask conditions.     

Heat of combustion of biofuels mixed with fossil diesel oil

The Brazilian government has presented a biofuel program, which aims the addition of 2% of biofuel in fossil diesel in 2008 and 5% up to 2013. Thus, the knowledge of heat of combustion of biofuel/diesel blends is necessary. The biodiesel was produced by transesterification of soybean oil with a yield of 87%. The diesel-like was obtained by pyrolysis of soybean oil. This biofuel presented all parameters according to ANP. The obtained heats of combustion were 41.36 ± 0.17; 38.70 ± 0.16; and 36.71 ± 0.17 MJ/kg for diesel, diesel-like and biodiesel, respectively. The results show that the heats of combustion of biofuels are approximately 17% smaller than fossil diesel. The obtained data also show that the heats of combustion depend on the methodology used for the biofuel production. Addition of biofuels to traditional diesel fuel results in a linear decreasing of the heat of combustion with the amount of the alternative fuel added to the diesel.     

A boundary corrected expansion of the moments of nearest neighbor distributions

In this article, the moments of nearest neighbor distance distributions are examined. While the asymptotic form of such moments is well‐known, the boundary effect has this far resisted a rigorous analysis. Our goal is to develop a new technique that allows a closed‐form high order expansion, where the boundaries are taken into account up to the first order. The resulting theoretical predictions are tested via simulations and found to be much more accurate than the first order approximation obtained by neglecting the boundaries. While our results are of theoretical interest, they definitely also have important applications in statistics and physics. As a concrete example, we mention estimating Rényi entropies of probability distributions. Moreover, the algebraic technique developed may turn out to be useful in other, related problems including estimation of the Shannon differential entropy.© 2010 Wiley Periodicals, Inc. Random Struct. Alg., 2010