Search Results
Application of molecular SERS nanosensors: where we stand and where we are headed towards?
Molecular specific and highly sensitive detection is the driving force of the surface-enhanced Raman spectroscopy (SERS) community. The technique opens the window to the undisturbed monitoring of cellular processes in situ or to the quantification of small molecular species that do not deliver Raman signals. The smart design of molecular SERS nanosensors makes it possible to indirectly but specifically detect, e.g. reactive oxygen species, carbon monoxide or potentially toxic metal ions. Detection schemes evolved over the years from simple metallic colloidal nanoparticles functionalized with sensing molecules that show uncontrolled aggregation to complex nanostructures with magnetic properties making the analysis of complex environmental samples possible. The present article gives the readership an overview of the present research advancements in the field of molecular SERS sensors, highlighting future trends. © 2020, The Author(s).
Selective Wacker type oxidation of a macrocyclic diene to the corresponding monounsaturated ketone used as fragrance
A selective reaction method for the efficient conversion of an isomeric mixture of 1,9-cyclohexadecadiene (1,9-CHDD) to the corresponding monounsaturated cyclohexadec-8-en-1-one (8-CHD) is described. 8-CHD was synthesized via Wacker type oxidation at room temperature using a highly electrophilic in situ formed dicationic palladium species. Isomerisation of the diene and over-oxidation of the substrate could be nearly suppressed by suitable reaction control, which has a positive effect on selectivity. The utilization of molecular oxygen as a green oxidant and environmentally benign iron(iii) salts as co-catalysts was successfully applied. This reaction strategy is promising to overcome the low overall reactivity of internal olefins in Wacker type oxidations. In addition, larger scale experiments showed further potential for industrial application. This journal is © 2019 The Royal Society of Chemistry.
Two-photon, visible light water splitting at a molecular ruthenium complex
Water splitting to give molecular oxygen and hydrogen or the corresponding protons and electrons is a fundamental four-electron redox process, which forms the basis of photosynthesis and is a promising approach to convert solar into chemical energy. Artificial water splitting systems have struggled with orchestrating the kinetically complex absorption of four photons as well as the difficult utilization of visible light. Based on a detailed kinetic, spectroscopic and computational study of Milstein's ruthenium complex, we report a new mechanistic paradigm for water splitting, which requires only two photons and offers a new method to extend the range of usable wavelengths far into the visible region. We show that two-photon water splitting is enabled by absorption of the first, shorter wavelength photon, which produces an intermediate capable of absorbing the second, longer wavelength photon (up to 630 nm). The second absorption then causes O–O bond formation and liberation of O2. Theoretical modelling shows that two-photon water splitting can be used to achieve a maximum solar-to-hydrogen efficiency of 18.8%, which could be increased further to 28.6% through photochemical instead of thermal H2 release. It is therefore possible to exceed the maximum efficiency of dual absorber systems while only requiring a single catalyst. Due to the lower kinetic complexity, intrinsic utilization of a wide wavelength range and high-performance potential, we believe that this mechanism will inspire the development of a new class of water splitting systems that go beyond the reaction blueprint of photosynthesis.
Intermetallic nickel silicide nanocatalyst—A non-noble metal–based general hydrogenation catalyst
Hydrogenation reactions are essential processes in the chemical industry, giving access to a variety of valuable compounds including fine chemicals, agrochemicals, and pharmachemicals. On an industrial scale, hydrogenations are typically performed with precious metal catalysts or with base metal catalysts, such as Raney nickel, which requires special handling due to its pyrophoric nature. We report a stable and highly active intermetallic nickel silicide catalyst that can be used for hydrogenations of a wide range of unsaturated compounds. The catalyst is prepared via a straightforward procedure using SiO2 as the silicon atom source. The process involves thermal reduction of Si–O bonds in the presence of Ni nanoparticles at temperatures below 1000°C. The presence of silicon as a secondary component in the nickel metal lattice plays the key role in its properties and is of crucial importance for improved catalytic activity. This novel catalyst allows for efficient reduction of nitroarenes, carbonyls, nitriles, N-containing heterocycles, and unsaturated carbon–carbon bonds. Moreover, the reported catalyst can be used for oxidation reactions in the presence of molecular oxygen and is capable of promoting acceptorless dehydrogenation of unsaturated N-containing heterocycles, opening avenues for H2 storage in organic compounds. The generality of the nickel silicide catalyst is demonstrated in the hydrogenation of over a hundred of structurally diverse unsaturated compounds. The wide application scope and high catalytic activity of this novel catalyst make it a nice alternative to known general hydrogenation catalysts, such as Raney nickel and noble metal–based catalysts.