Michał Cegłowski

Synthesis of new dendritic antenna-like polypyridine ligands

An efficient synthesis of multidentate polypyridine ligands, 3,5-bis(2,2′-bipyridin-4-ylethynyl)benzoic acid and 3,5-bis(2,5-bis(2-pyridyl)-pyridin-4-ylethynyl)benzoic acid, with potential application in the production of ruthenium dyes for dye-sensitised solar cells was developed. Isolation of intermediate products and final compounds is simple and the yields are very high. The ligands obtained can be used in the synthesis of dendritic analogues of well known and very efficient N3 dye and “black dye”.

Dielectric barrier discharge ionization in characterization of organic compounds separated on thin-layer chromatography plates.

A new method for on-spot detection and characterization of organic compounds resolved on thin layer chromatography (TLC) plates has been proposed. This method combines TLC with dielectric barrier discharge ionization (DBDI), which produces stable low-temperature plasma. At first, the compounds were separated on TLC plates and then their mass spectra were directly obtained with no additional sample preparation. To obtain good quality spectra the center of a particular TLC spot was heated from the bottom to increase volatility of the compound. MS/MS analyses were also performed to additionally characterize all analytes. The detection limit of proposed method was estimated to be 100 ng/spot of compound.

Molecular scavengers as carriers of analytes for mass spectrometry identification.

Storage and preconcentration of various molecules by molecular scavengers for thermal desorption and identification by mass spectrometry is presented. A dielectric barrier discharge ionization source combined with a heating element for the chemical characterization of amines and organic acids, initially trapped by molecular scavengers, is described. The developed technique can be applied for preconcentration of minute amounts of molecules in liquid and gaseous phases, as well as their transportation and thorough analysis. The method, operating at ambient pressure, can also be complementary to electron impact ionization, with no need for sample derivatization.

Functionalization of gold-coated carbon nanotubes with self-assembled monolayers of thiolates

Multi-walled carbon nanotubes (CNT) were synthesized by chemical vapor deposition using Co–Fe as a catalyst and ethylene as a carbon source. Afterward, a simple method combining wet-chemistry and chemical reduction was used to prepare carbon nanotube/gold material (CNT/Au). Pristine nanotubes and CNT/Au were characterized by transmission electron microscopy micrographs. It appeared that gold formed nanoparticles on CNTs endings and their sidewalls. Further functionalization was carried out by using thiols of different chemical properties and molecule sizes. Thiols formed self-assembled monolayer on gold surface that led to formation of CNT/gold/thiol-functionalized material. The amounts of chemisorbed thiols were measured by elemental analysis and thermogravimetry.

Laser desorption/ionization mass spectrometric analysis of surfactants on functionalized carbon nanotubes

RATIONALE Recently, unmodified and carboxylated carbon nanotubes have been used as assisting surfaces laser desorption/ionization (LDI) in mass spectrometry. The functionalization of carbon nanotubes with organic compounds should lead to a gamut of other promising LDI-assisting surfaces. METHODS Carboxylated carbon nanotubes were functionalized with sinapinic acid either covalently or by creating an ionic macro-complex. Polyether-based surfactants were used as analytes to examine the properties of these new matrices. Mass spectrometric analysis was conducted on a LDI-quadrupole time-of-flight (QTOF) mass spectrometer. Carbon nanotube surfaces were deposited from suspension using the dried-droplet method. RESULTS The functionalization of the carbon nanotubes was confirmed with Fourier transform infrared (FTIR) spectroscopy. The usefulness of each material was examined with two poly(ethylene glycol) hexadecyl ether amphiphiles (Brij® 52 and Brij® 56) and a poly(ethylene glycol) monomethyl ether as analytes. Generally, the mass spectra obtained with carbon nanotubes covalently functionalized with sinapinic acid as a matrix had peaks with higher intensities than those obtained with carbon nanotubes functionalized by ionic macro-complex formation. CONCLUSIONS The presented new materials based on functionalized carbon nanotubes are effective in the LDI mass analysis of polyether amphiphiles and poly(ethylene glycol) monomethyl ether. This type of assisting surfaces can be highly modified by appropriate functionalization procedures.

Laser desorption/ionization mass spectrometric analysis of folic acid, vancomycin and Triton® X-100 on variously functionalized carbon nanotubes.

RATIONALE Carbon nanotubes (CNTs) have been ascertained to constitute versatile assisting matrices for laser desorption/ionization mass spectrometric analysis of different molecules. The functionalization thereof can lead to obtaining laser desorption/ionization assisting surfaces that would allow the detection of molecules at lower concentration and produce spectra with a better signal-to-noise ratio. METHODS Pristine, -OH and -COOH functionalized multi-walled CNTs were obtained from commercial suppliers. Gallic or sinapinic acid was attached covalently to the CNT surfaces by forming an ester bond. Folic acid, vancomycin and Triton(®) X-100 were used as analytes to examine properties of these new assisting surfaces. Mass spectrometry analysis was conducted on a matrix-assisted laser desorption/ionization quadrupole time-of-flight (MALDIQTOF) mass spectrometer. RESULTS The functionalization of CNTs was confirmed with Fourier transform infrared (FTIR) spectroscopy. The obtained mass spectra revealed that all the assisting surfaces are capable of transferring energy to the analytes; moreover, the presence of carboxyl groups in the structures of CNTs highly enhances their ionization properties. Nevertheless, the presence of sinapinic acid on CNT surfaces does not increase their properties to absorb pulse laser energy. CONCLUSIONS The presented assisting surfaces are effective in LDI mass analysis of folic acid, vancomycin and Triton(®) X-100. The appropriate functionalization of CNTs can lead to the production of assisting surfaces that can become highly effective in the ionization of particular types of analytes.

New gel-like polymers as selective weak-base anion exchangers.

A group of new anion exchangers, based on polyamine podands and of excellent ion-binding capacity, were synthesized. The materials were obtained in reactions between various poly(ethyleneamines) with glycidyl derivatives of cyclotetrasiloxane. The final polymeric, strongly cross-linked materials form gel-like solids. Their structures and interactions with anions adsorbed were studied by spectroscopic methods (CP-MAS NMR, FR-IR, UV-Vis). The sorption isotherms and kinetic parameters were determined for 29 anions. Materials studied show high ion capacity and selectivity towards some important anions, e.g., selenate(VI) or perrhenate.

Copper complexes formed by 3,5-bis(2,2′-bipyridin-4-ylethynyl)benzoic acid and its methyl and ethyl esters as studied by electrospray ionization mass spectrometry

AbstractElectrospray ionization mass spectrometry was used to study the complexes of ligands containing two bipyridine units, namely 3,5-bis(2,2-bipyridin-4-ylethynyl)benzoic acid (1) and its methyl and ethyl esters (2, 3), with copper cation, with CuCl2 as a source of copper. It was found that the type of complexes formed strongly depends on CuCl2 concentration. At lower CuCl2 concentration, the detected complexes were rather simple and some of them were formed upon electrospray ionization conditions e.g. ions [22+Cu2]2+ and [32+Cu2]2+ (complexes ligand-Cu(I) of stoichiometry 2:2) which are analogical to the well known, for quaterpyridine, helical complexes. At higher CuCl2 concentration, the detected complexes were more complicated, and most of them contained copper cations bridged by chlorides. The largest ions were [L2+Cu4Cl6]2+. The CID MS/MS spectra of these ions allowed determination of their mass spectrometric fragmentation pathways and as a consequence their structure elucidation.

Determination of conditional stability constants for phytic acid complexes with Mg(2+), Ca(2+) and Zn(2+) ions using electrospray ionization mass spectrometry.

The electrospray ionization mass spectrometry competitive method has been used for the determination of the conditional stability constants of phytic acid complexes with Mg2+, Ca2+ and Zn2+ ions. The competing complexation between ethylenediaminetetraacetic acid (EDTA) and phytic acid was studied. For EDTA complexes with Mg2+, Ca2+ and Zn2+ ions, the values of the conditional stability constants are known and were used for the calculation of this constant for the phytic acid complexes. The values obtained are in agreement with the literature data. The method applied permitted a fast and simple determination of conditional stability constants by measuring the response of the ionized coordination complexes.

Unexpected formation of [M] 2+ from [M+CuCl+H] 2+ ions under CID conditions, where M is a moleculeof 3,5-bis(2,2’-bipyridin-4-ylethynyl)benzoic acidor its methyl ester

Abstract [M+CuCl+H]2+ ions were generated using electrospray ionization (ESI); where M is a molecule of 3,5-bis(2,2’-bipyridin-4-ylethynyl)benzoic acid or its methyl ester (1 and 2, respectively). The ions were subjected to CID-MS/MS analysis. It was found that their gas phase decomposition lead to the formation of rare di-cations [M]2+, namely [1]2+ and [2]2+ ions. The formation of [1]2+ ion from [3+H+CuCl]2+ ion in the second fragmentation, where 3 is ethyl ester of 3,5-bis(2,2-bipyridin-4-ylethynyl)benzoic acid, was also observed since in the first fragmentation step the loss of ethylene molecule from [3+H+CuCl]2+ ion took place. To the best of our knowledge, it is the first time that [M]2+ ions formation from respective metal complexes has been reported. It is also unusual that formation of [M]2+ ions is not accompanied by formation of [M]+∙ ions. Furthermore, as expected, theoretical calculation and electron ionization mass spectra show that 1 and 2 are not especially prone to form [M]2+ ions. Thus formation of [M]2+ ions under CID conditions is very surprising. Graphical Abstract