New Automated and High-Throughput Quantitative Analysis of Urinary Ketones by Multifiber Exchange-Solid Phase Microextraction Coupled to Fast Gas Chromatography/Negative Chemical-Electron Ionization/Mass Spectrometry

The present research is focused on automation, miniaturization, and system interaction with high throughput for multiple and specific Direct Immersion-Solid Phase Microextraction/Fast Gas Chromatography analysis of the urinary ketones. The specific Mass Spectrometry instrumentation, capable of supporting such the automated changeover from Negative Chemical to Electron Ionization mode, as well as the automation of the preparation procedure by new device called MultiFiber Exchange, through change of the fibers, allowed a friendly use of mass spectrometry apparatus with a number of advantages including reduced analyst time and greater reproducibility (2.01–5.32%). The detection limits for the seven ketones were less than 0.004 mg/L. For an innovative powerful meaning in high-throughput routine, the generality of the structurally informative Mass Spectrometry fragmentation patterns together with the chromatographic separation and software automation are also investigated

An Insoluble Polymer-bound Phosphoramidite For The Copper-catalysed Enantioselective 1,4-addition Of ZnEt2 To 2-cyclohexenone

The preparation of a chiral phosphoramidite ligand anchored to a Merrifield resin has been studied and its use in the copper-catalysed heterogeneous enantioselective conjugate addition of ZnEt2 to 2-cyclohexenone investigated. The insoluble polymer bound ligand could be recovered quantitatively by filtration, affording e.e. values in the range 65–84% in the course of successive recycle runs.

Step-by-Step Growth of HKUST-1 on Functionalized TiO2 Surface: An Efficient Material for CO2 Capture and Solar Photoreduction

The present study reports on a simple preparation strategy of a hybrid catalyst, TiO2/HKUST-1, containing TiO2 anatase nanoparticles (NPs) with tailored morphology and photocatalytic activity coupled with a porous metal-organic framework (MOF), namely HKUST-1, as an advanced material for the CO2 photocatalytic reduction. In detail, TiO2/HKUST-1 catalyst was prepared via an easy slow-diffusion method combined with a step-by-step self-assembly at room temperature. The growth of crystalline HKUST-1 onto titania surface was achieved by functionalizing TiO2 nanocrystals, with phosphoesanoic acid (PHA), namely TiO2-PHA, which provides an intimate contact between MOF and TiO2. The presence of a crystalline and porous shell of HKUST-1 on the TiO2 surfaces was assessed by a combination of analytical and spectroscopic techniques. TiO2/HKUST-1 nanocomposite showed a significant efficiency in reducing CO2 to CH4 under solar light irradiation, much higher than those of the single components. The role of MOF to improve the photoreduction process under visible light was evidenced and attributed either to the relevant amount of CO2 captured into the HKUST-1 porous architecture or to the hybrid structure of the material, which affords enhanced visible light absorption and allows an effective electron injection from TiO2-PHA to HKUST-1, responsible for the photochemical reduction of CO2

Biomass Waste-Derived Pd-PiNe Catalyst for the Continuous-Flow Copper-Free Sonogashira Reaction in a CPME-Water Azeotropic Mixture

6nononeHerein, we report on the development of a waste minimization/valorization methodology applied to the representative benchmark Sonogashira cross-coupling reaction performed in a continuous-flow reactor, featuring a continuous-flow downstream membrane organic/aqueous separator to recover medium and products with minimal waste. The protocol is based on the use of a biomass waste-derived heterogeneous Pd-based catalyst, which is obtained from the valorization of urban-waste pine needles (PiNe). In a circular economy approach, the PiNe biomass has been proven to be capable of producing an effective active carbon support for Pd nanoparticle immobilization. In addition, the catalyst has been utilized in an azeotropic mixture formed by industrial waste-derived cyclopentyl methyl ether (CPME) and water. Thanks to this combination and with the adoption of flow conditions, high yields of final target products could be accessed with high stability and durability of the catalyst. Final isolation of the products has been realized by setting an in-line liquid-liquid separator in flow, which has also allowed CPME recovery with a significant reduction of the waste generated. The protocol has been applied to the representative preparation of eniluracil, a GSK API.restrictedFerlin F.; Valentini F.; Sciosci D.; Calamante M.; Petricci E.; Vaccaro L.Ferlin, F.; Valentini, F.; Sciosci, D.; Calamante, M.; Petricci, E.; Vaccaro, L

The Stille Reaction: Applications in the Synthesis of Organic Dyes for DSSCs

The cross-coupling reaction of organic electrophiles with organostannanes, traditionally known as the Stille reaction, has found renewed interest in the preparation of new organic materials such as conjugated polymers, organic semiconductors and photoactive molecules for use in organic photovoltaics. Moreover, a very recent field in which the Stille reaction has found successful application is that of the design and synthesis of new photosensitizers for dye-sensitized solar cells (DSSCs). DSSCs are considered a promising alternative for energy production from renewable sources. In such devices light harvesting is carried out by a dye which is generally a highly conjugated molecule. Due to the mild operating conditions and the high functional-group compatibility, the Stille reaction proved to be a powerful tool not only for the preparation of photosensitizers, but also to plan their chemical elaboration in order to tune and optimize their photophysical, electrochemical and photovoltaic properties. In this microreview some recent examples of the Stille reaction in the synthesis of organic dyes for DSSC are reported

In water alkylation of amines with alcohols through a borrowing hydrogen process catalysed by ruthenium nanoparticles

A simple and environmentally benign procedure for the synthesis of secondary amines in water has been developed. Combining Ru3(CO)12, tetraphenylcyclopentadienone and a small quantity of TGPS-750-M surfactant, primary and secondary alcohols were alkylated at N employing equimolar amounts of aromatic amines in water. The reaction occurs under microwave (MW) dielectric heating with high conversion and high yield. When required, the use of biomass-derived 2-MeTHF or GVL as a co-solvent is possible. Under the influence of MWs, a Ru nanoparticle–nanomicelle combination was formed acting as an effective and recyclable catalyst. This protocol was also employed for “in water” cyclisation to synthesise biologically relevant pyrrolobenzodiazepines (PBDs).

Synthesis and Characterization of New Organic Dyes Containing the Indigo Core

A new series of symmetrical organic dyes containing an indigo central core decorated with different electron donor groups have been prepared, starting from Tyrian Purple and using the Pd-catalyzed Stille-Migita coupling process. The effect of substituents on the spectroscopic properties of the dyes has been investigated theoretically and experimentally. In general, all dyes presented intense light absorption bands, both in the blue and red regions of the visible spectrum, conferring them a bright green color in solution. Using the same approach, an asymmetrically substituted D–A-π–A green dye, bearing a triarylamine electron donor and the cyanoacrylate acceptor/anchoring group, has been synthesized for the first time and fully characterized, confirming that spectroscopic and electrochemical properties are consistent with a possible application in dye-sensitized solar cells (DSSC)