Identification of Bremia lactucae and Oidium neolycopersici proteins extracted for intact spore MALDI mass spectrometric biotyping

Several proteomic approaches were applied to identify protein markers providing typical signals during intact cell/spore (IC/IS) MALDI‐TOF MS of two plant pathogens, namely Bremia lactucae (a downy mildew) and Oidium neolycopersici (a powdery mildew). First, proteins were extracted from intact spores of the microorganisms under conditions simulating their treatment prior to the mass spectrometric analysis. After a separation by electrophoresis and tryptic digestion, 198 and 140 proteins were identified in the B. lactucae and O. neolycopersici extracts, respectively. A large portion of them were found to be involved in the process of protein biosynthesis. For the first time, some proteins were assigned to characteristic signals in MS profiles of the investigated pathogens based on an agreement in the molecular mass. There were 9 and 10 proteins recognized, respectively, which could contribute significantly to the spectral patterns. These proteins were assigned tentatively to the following peaks in the MS profiles: (i) m/z 7828; 8593; 10 456; 11 312; 12 450; 12 763; 14 756 and 16 854 for B. lactucae; (ii) m/z 7709; 8895; 9504; 9952; 11 317; 14 082 and 14 839 for O. neolycopersici. We demonstrated the presence of ribosomal proteins and histones, which could be employed as markers in biotyping analyses for pathogen identification.     

Front Cover: Creating Hydrophobic Foils From Biopolymer Blends Using Mechanical Microimprinting (ChemPhysChem 20/2023)

The surface topography of biodegradable polymer foils is modified by mechanical imprinting on a submillimeter length scale. The created patterns strongly influence the wetting behavior and allow the preparation of hydrophobic surfaces with controlled solid-liquid interaction. A detailed analysis of anisotropic surface patterns reveals that the observed effect arises from a combination of topographical and compositional changes that are introduced to the surface. As a main result it is found that an individual combination of material and structure is required for the production of water-repellent biopolymer foils that are highly attractive for packaging applications.     

Low-dimensional compounds containing bioactive ligands. XXII. First crystal structure,cytotoxic activity and DNA and HSA binding of a zirconium(IV) complex with 8-hydroxyquinoline-2-carboxylic acid

A new zirconium(IV) complex, diaquabis(8-hydroxyquinoline-2-carboxylato-κ³N,O²,O⁸)zirconium(IV) dimethylformamide disolvate, [Zr(C₁₀H₅NO₃)₂(H₂O)₂]·2C₃H₇NO or [Zr(QCa)₂(H₂O)₂]·2DMF ( 1 ) (HQCaH is 8-hydroxyquinoline-2-carboxylic acid and DMF is dimethylformamide), was prepared and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray structure analysis. Complex 1 is a mononuclear complex in which the Zr^IV atoms sit on the twofold axis and they are octacoordinated by two N and six O atoms of two tridentate anionic QCa²⁻ ligands, and two aqua ligands. Outside the coordination sphere are two DMF molecules bound to the complex unit by hydrogen bonds. The structure and stability of complex 1 in dimethyl sulfoxide were verified by NMR spectroscopy. The cytotoxic properties of 1 and HQCaH were studied in vitro against eight cancer cell lines, and their selectivity was tested on the BJ-5ta noncancerous cell line. Both the complex and HQCaH exhibited low activity, with IC₅₀ > 200 µM. DNA and human serum albumin (HSA) binding studies showed that 1 binds to calf thymus (CT) DNA via intercalation and is able to bind to the tryptophan binding site of HSA (Trp-214).     

Thermodynamic study of lanthanide(III) complexes with bifunctional monophosphinic acid analogues of H4dota and comparative kinetic study of yttrium(III) complexes

New bifunctional H(4)dota-like ligands with three acetic acid and one phosphinic acid pendant arms and propionate (H(5)do3ap(PrA)) or 4-aminobenzyl (H(4)do3ap(ABn)) reactive groups bound to the phosphorus atom were investigated. Potentiometric studies showed that the ligands have a similar basicity to the parent H(4)dota and the stability constants of their complexes with sodium(i) and selected lanthanide(III) ions are also similar. Formation and acid-assisted decomplexation kinetics of yttrium(III) complexes with a series of H(4)dota-like ligands (H(4)dota and its phosphinic/phosphonic acid analogues) were studied and the reactions are sensitive to a slight modification of the ligand structure. The (2-carboxyethyl)phosphinic acid derivative H(5)do3ap(PrA) and the phosphonic acid ligand H(5)do3ap form complexes faster than H(4)dota. The most kinetically inert complex is that with H(4)do3ap(ABn). Rates of complexation and decomplexation can depend on the ability to transfer proton(s) outside/inside the complex cavity and, therefore, on the hydrophobicity of the ligands. The results demonstrate that the new bifunctional ligands are suitable for labelling biomolecules with yttrium(iii) radioisotopes for utilization in nuclear medicine.     

Simple synthesis of calix[4]arenes in a 1,2-alternate conformation

The least accessible calix[4]arene conformers-1,2-alternates-can be very easily prepared using a proximal dialkylation and subsequent peralkylation reaction sequence.     

UV Raman spectroscopy--a technique for biological and mineralogical in situ planetary studies

We report on the great advantages of using deep UV Raman system for in situ planetary applications. Among them are to be mentioned: (I) higher scattering efficiency compared to VIS-IR Raman excitation wavelengths, (II) electronic resonance effects which increase the intrinsically weak Raman signal thus improving the S/N ratio of the detected Raman signals and (III) spectral separation of Raman and fluorescence signals. All these advantages are making UV Raman a valuable technique for in situ planetary applications. Mineral as well as biological samples were analyzed using Raman deep UV excitation and the results are presented. For the mineral samples a comparison with excitation in the NIR-VIS spectral regions is made. The impact of fluorescence on Raman data acquisition at different laser excitation wavelengths is assessed. Making use of the resonance effects, spectra of microorganisms were recorded with a high S/N ratio, allowing afterwards a very precise identification and classification (to the strain level) of the measured samples.     

Combination of chemical and electron-impact ionisation with GC×GC–qMS for characterization of fatty alcohol alkoxylate polymers in the low-molecular-weight range up to 700 Da

The class of fatty alcohol alkoxylates describes surfactants that are synthesised by reaction of fatty alcohols with alkoxides such as ethylene oxide or propylene oxide or a combination of both as copolymers. Such alkoxylates are used, for example, as nonionic surfactants in home and industrial cleaning and washing agents. Chemical characteristics of such alkoxylate copolymers, for example the degree of alkoxylation, the arrangement of building blocks (random or block polymerisation), the type of the starter, and endcapping, play an important role in application behaviour. The analysis of these characteristics is challenging because in many cases such copolymers have high polydispersity and a large number of constitutional isomers depending on the degree of alkoxylation. Furthermore, the alkoxylates often occur in a complex multicomponent matrix. Here we present a method for characterization of silylated fatty alcohol alkoxylates in the low-molecular-weight range by means of comprehensive two-dimensional gas chromatography–mass spectrometry with electron impact and chemical ionisation. This method also enables detailed analysis of the alkoxylates in a complex matrix such as modern detergents.