A method of increasing the sensitivity for laser desorption in an ion trap mass spectrometer

Laser desorption in an ion trap mass spectrometer shows significant promise for both qualitative and trace analysis. In this work, we explore various combinations of time-varying DC and radiofrequency (RF) fields in order to optimize laser-generated signals. By judicious choice of timing between the laser desorption pulse and the rise in the applied RF trapping potential, we observed over an order of magnitude enhancement in the trapped ion signal. This new method for laser desorption has enabled us to observe mass spectra of many compounds (e.g., pyrene, dichlorobenzene, and ferrocene) that are barely detectable using previous laser desorption methods. Effects of laser timing and the magnitude of the steady-state RF potential are discussed.     

Microwave-Assisted Conversion of Carbohydrates

Catalytic conversion of carbohydrates into value-added products and platform chemicals became a trend in recent years. Microwave activation used in the processes of carbohydrate conversion coupled with the proper choice of catalysts makes it possible to enhance dramatically the efficiency and sometimes the selectivity of catalysts. This mini-review presents a brief literature survey related to state-of-the-art methods developed recently by the world research community to solve the problem of rational conversion of carbohydrates, mostly produced from natural resources and wastes (forestry and agriculture wastes) including production of hydrogen, synthesis gas, furanics, and alcohols. The focus is made on microwave technologies used for processing carbohydrates. Of particular interest is the use of heterogeneous catalysts and hybrid materials in processing carbohydrates.     

Transition Metal Substituted Barium Hexaferrite-Modified Electrode: Application as Electrochemical Sensor of Acetaminophen

This study used substituted barium hexaferrites, which were previously prepared and reported by the authors, to detect acetaminophen by the modification of a conventional glassy carbon electrode (GCE), which led to promising results. The synthesis of this electrode-modifying material was conducted using a citrate sol gel process. A test synthesis using glycerin and propylene glycol revealed that glycerin produced a better result, while less positive anodic potential values were associated with the electrooxidation of N-acetyl-p-aminophenol (NAP). Excellent electroactivity was exhibited by the cobalt-substituted barium-hexaferrite-nanomaterial-modified electrode. A good linear relationship between the concentration and the current response of acetaminophen (paracetamol) was obtained with a detection limit of (0.255 ± 0.005) µM for the Ba_1.0Co_1.22Fe_11.41O_18.11 GCE, (0.577 ± 0.007) µM for the Ba_1.14Cu_0.82Fe_11.65O_18.02 GCE, and (0.595 ± 0.008) µM for the bare GCE. The levels of NAP in a real sample of urine were quantitatively analyzed using the proposed method, with recovery ranges from 96.6% to 101.0% and 93.9% to 98.4% for the modified electrode with Cobalt-substituted barium hexaferrites (CoF_M) and Copper-substituted barium hexaferrites (CuF_M), respectively. These results confirm the high electrochemical activity of Ba_1.0Co_1.22Fe_11.41O_18.11 nanoparticles and thus their potential for use in the development of sensing devices for substances of pharmaceutical interest, such as acetaminophen (NAP).     

Versatile post-functionalisation strategy for the formation of modular organic–inorganic polyoxometalate hybrids

Hybrid structures incorporating different organic and inorganic constituents are emerging as a very promising class of materials since they synergistically combine the complementary and diverse properties of the individual components. Hybrid materials based on polyoxometalate clusters (POMs) are particularly interesting due to their versatile catalytic, redox, electronic, and magnetic properties, yet the controlled incorporation of different clusters into a hybrid structure is challenging and has been scarcely reported. Herein we propose a novel and general strategy for combining multiple types of metal-oxo clusters in a single hybrid molecule. Two novel hybrid POM structures (HPOMs) bis-functionalised with dipentaerythritol (R–POM₁–R; R = (OCH₂)₃CCH₂OCH₂C(CH₂OH)) were synthesised as building-blocks for the formation of heterometallic hybrid triads (POM₂–R–POM₁–R–POM₂). Such a modular approach resulted in the formation of four novel heterometallic hybrids combing the Lindqvist {V₆}, Anderson–Evans {XMo₆} (X = Cr or Al) and trisubstituted Wells–Dawson {P₂V₃W₁₅} POM structures. Their formation was confirmed by multinuclear Nuclear Magnetic Resonance (NMR), infrared (IR) and UV-Vis spectroscopy, as well as Mass Spectrometry, Diffusion Ordered Spectroscopy (DOSY) and elemental analysis. The thermal stability of the hybrids was also examined by Thermogravimetric Analysis (TGA), which showed that the HPOM triads exhibit higher thermal stability than comparable hybrid structures containing only one type of POM. The one-pot synthesis of these novel compounds was achieved in high yields in aqueous and organic media under simple reflux conditions, without the need of any additives, and could be translated to create other hybrid materials based on a variety of metal-oxo cluster building-blocks.

A versatile modular approach has been developed for incorporating different metal-oxo nanoclusters with characteristic structures into a single hybrid molecule by covalently linking them with polyol ligands.     

Analysis of large experimental datasets in electrochemical impedance spectroscopy

An approach for the analysis of large experimental datasets in electrochemical impedance spectroscopy (EIS) has been developed. The approach uses the idea of successive Bayesian estimation and splits the multidimensional EIS datasets into parts with reduced dimensionality. Afterwards, estimation of the parameters of the EIS-models is performed successively, from one part to another, using complex nonlinear least squares (CNLS) method. The results obtained on the previous step are used as a priori values (in the Bayesian form) for the analysis of the next part. To provide high stability of the sequential CNLS minimisation procedure, a new hybrid algorithm has been developed. This algorithm fits the datasets of reduced dimensionality to the selected EIS models, provides high stability of the fitting and allows semi-automatic data analysis on a reasonable timescale. The hybrid algorithm consists of two stages in which different zero-order optimisation strategies are used, reducing both the computational time and the probability to overlook the global optimum. The performance of the developed approach has been evaluated using (i) simulated large EIS dataset which represents a possible output of a scanning electrochemical impedance microscopy experiments, and (ii) experimental dataset, where EIS spectra were acquired as a function of the electrode potential and time. The developed data analysis strategy showed promise and can be further extended to other electroanalytical EIS applications which require multidimensional data analysis.     

New indole trimers as precursors for molecular electronic materials

We have prepared two new C₃-symmetric, substituted-triazatruxene molecules using a facile one-pot trimerisation of 5-carboxyindole and 6-bromoindole in acetic acid using Br₂, giving 2a and 3a, respectively. These were subsequently modified by the addition of six alkyl chains to the N- and carboxyl-positions of 2a giving 2b and three alkyl chains to the N-positions of 3a giving 3b. The new molecules were characterised using cyclic voltammetry, UV/vis and emission spectroscopy, DFT calculations and in the case of 3b, field-effect transistor measurements showing gate-modulated source-drain current. These represent a straightforward route to large polyaromatic molecules with easily-modified side groups and are suitable as building blocks for synthesis of functional molecules for materials.     

Regioselective Arylation and Alkynylation of 2,3‐Dibromo‐1H‐inden‐1‐one by Suzuki?Miyaura and Sonogashira Cross‐Coupling Reactions

Suzuki? Miyaura reactions of 2,3‐dibromo‐1H‐inden‐1‐one afforded a wide range of arylated 1H‐inden‐1‐ones. Sonogashira cross‐coupling reactions gave alkynylated indenones. The reactions proceeded with very good regioselectivity in the less sterically hindered and more electron‐deficient position 3.