Wojciech Ciesielski

The effect of the number of alkyl substituents on imidazolium ionic liquids phytotoxicity and oxidative stress in spring barley and common radish seedlings.

Increasing amounts of two ILs: 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6] and 1-butyl-2,3-dimethylimidazolium hexafluorophosphate [BMMIM][PF6], were introduced to soil in which spring barley (Hordeum vulgare) and common radish (Raphanus sativus L. subvar. radicula Pers.) seedlings were cultivated, in order to evaluate the phytotoxicity of ionic liquids with imidazolium cation with two or three alkyl substituents attached. The results of the study i.e. the inhibition of the length of plants and their roots, as well as the yield of fresh weight of plants, clearly showed that differences in the number of substituents did not affect the toxicity of these ILs. Although, radish was more resistant to the applied ionic liquids than barley. Ionic liquids led to a decrease in the content of all assimilation pigments and induced oxidative stress in the plants, as showed by an increase in malondialdehyde (MDA) content, and changes in the level of H2O2 and antioxidant enzymes: superoxide dismutase (SOD), catalase (CAT) and peroxidase (POD). The best biomarkers of oxidative stress in both plants were the changes in chlorophyll content and the increase in POD activity. Both spring barley and radish exposed to [BMIM][PF6] and [BMMIM][PF6] accumulated a large amount of fluoride ions, which further increased the toxicity of these compounds for both plants.

β-Cyclodextrin/protein conjugates as a innovative drug systems: synthesis and MS investigation

The design of proteins whose structure and function can be manipulated by binding with specific ligands such as cyclodextrins, has been of great interest in the field of protein engineering and also could be used as drug delivery systems in targeted cancer therapy (Loftsson and Duchêne, Int. J. Pharm. 329:1–11, 1; Loftsson et al., Expert. Opin. Drug Deliv. 2:335–351, 2). CD/proteins conjugates are synthesized using original high temperature method in which mono-6-O-formyl-β-CD reacts with two proteins: basic pancreatic trypsin inhibitor and lysozyme. The proposed synthesis method has a high reproducibility which makes it useful for pharmaceutical purposes. That method allows to obtain the conjugate without losing protein’s biological and enzymatic activity which will used in the reaction, and without violating the chemical structure of cyclodextrin molecules.

E FFECTIVENESS OF INTRINSIC BIODEGRADATION ENHANCEMENT IN OIL HYDROCARBONS CONTAMINATED SOIL

Abstract Studies were conducted using a 10-chamber Micro-Oxymax (Columbus, OH, USA) respirometer to determine the effect of bioaugmentation, biostimulation and combination of them on enhancing intrinsic biodegradation of oil hydrocarbons in soil. Contaminated soil was collected from a former military airport in Kluczewo, Poland. Bioaugmentation was realized by addition of indigenous or exogenous bacteria to soil. Biostimulation was done by aerated water supply and surfactant addition. Bioaugmentation + addition of a surfactant was applied as the combined treatment. The intrinsic and enhanced hydrocarbons biodegradation rates were estimated from the slopes of linear regressions of cumulative curves of O2 uptake. Pertinent biodegradation rates were recalculated on the basis of the stoichiometric reaction (mass balance equation) and conversion equation. The results showed that combined treatment (indigenous bacteria bioaugmentation + addition of a surfactant) was the most effective method of biodegradation enhancement as the 20-fold increase of biodegradation rate was observed. Streszczenie Przeprowadzono badania mające na celu określenie efektywności wspomagania biodegradacji węglowodorów ropopochodnych w gruncie w wyniku zastosowania bioaugmentacji, biostymulacji lub metody kombinowanej. Próbki gruntu użyte do badań zostały pobrane z terenu Centralnej Stacji Tankowania (CST) lotniska Kluczewo niedaleko Stargardu Szczecińskiego. Bioaugmentację przeprowadzono z użyciem autochtonicznych i allochtonicznych mikroorganizmów zdolnych do rozkładu węglowodorów ropopochodnych. Z kolei biostymulacja obejmowała wprowadzenie napowietrzonej wody lub substancji powierzchniowo czynnej (SPC) do zanieczyszczonego gruntu. Biodegradację węglowodorów ropopochodnych szacowano na podstawie konsumpcji O2 przyużyciu respirometru Micro-Oxymax V6.0 COLUMBUS INSTRUMENTS. Średnie szybkości konsumpcji O2 podczas biodegradacji węglowodorów wyznaczono z równań aproksymacji liniowej krzywych kumulacyjnych.Na podstawie równania bilansu masy i wyznaczonych szybkości konsumpcji O2 obliczono szybkość biodegradacji węglowodorów, tj. szybkość ubytku substratu w czasie. Z przeprowadzonych badań wynika, że metoda kombinowana (kombinacja bioaugmentacji z dodatkiem SPC) była najbardziej efektywną metodą wspomagania biodegradacji węglowodorów ropopochodnych w gruncie - odnotowano wtedy 20-krotny wzrost szybkości biodegradacji.

Starch–metal complexes and their rheology

Abstract Changes in conductivity of 5 w/w% starch gels was studied on their titration with 0.1 M aqueous solutions of selected metal salts. Starch gels usually trapped around 10 mg metal ions per 1 g starch [Co(II), Cu(II), Fe(III), Ni(II)] and that value was only slightly dependent on starch origin (amaranthus, corn, potato, tapioca, waxy corn). Among salts studied (acetates, chlorides, nitrates) FeCl3 and NiCl2 were likely to be used because they hydrolyzed increasing conductivity of the solutions and formed micelles of corresponding hydroxides adhering to starch micelles and increasing amount of trapped metal. Addition of metal salts to starch gels had a devastating effect on pseudoplasticity and viscosity of starch gels and only potato starch gel was to a certain extent, exceptional in that respect.

Triphenylmethanethiol as a Precursor for the Simultaneous Formation of Bis (Triphenylmethyl) Sulfide, Bis(Triphenylmethyl) Trisulfide, and Bis(Triphenylmethyl) Peroxide: Crystal Structures and Hirshfeld Surface Analyses

Abstract Structurally identified, three unexpected products, obtained from the reaction of tritphenylmethanethiol with (+)-R-pulegone, i.e., bis(triphenylmethyl) sulfide, bis(tripheny- lmethyl) trisulfide, and bis(triphenylmethyl) peroxide, have been examined using Hirshfeld surface analysis. This analysis has been also performed for several of their simple analogues. Comparison of the results obtained shows that relative contributions of close contacts to the Hirshfeld surfaces of the molecules depend on the number of sulfur atoms between the central C atoms of compounds Ph3CSnCPh3 (n = 1, 2, 3 and 6), and in the case of Ph3XO2XPh3 (X = C, Si, Ge) compounds on the type of central X atom. GRAPHICAL ABSTRACT

New quaternary carbide Mg1.52Li0.24Al0.24C0.86 as a disorder derivative of the family of hexa­gonal close-packed (hcp) structures and the effect of structure modification on the electrochemical behaviour of the electrode

Magnesium alloys are the basis for the creation of light and ultra-light alloys. They have attracted attention as potential materials for the accumulation and storage of hydrogen, as well as electrode materials in metal-hydride and magnesium-ion batteries. The search for new metal hydrides has involved magnesium alloys with rare-earth transition metals and doped by p- or s-elements. The synthesis and characterization of a new quaternary carbide, namely dimagnesium lithium aluminium carbide, Mg1.52Li0.24Al0.24C0.86, belonging to the family of hexagonal close-packed (hcp) structures, are reported. The title compound crystallizes with hexagonal symmetry (space group P-6m2), where two sites with -6m2 symmetry and one site with 3m. symmetry are occupied by an Mg/Li statistical mixture (in Wyckoff position 1a), an Mg/Al statistical mixture (in position 1d) and C atoms (2i). The cuboctahedral coordination is typical for Mg/Li and Mg/Al, and the C atom is enclosed in an octahedron. Electronic structure calculations were used for elucidation of the ability of lithium or aluminium to substitute magnesium, and evaluation of the nature of the bonding between atoms. The presence of carbon in the carbide phase improves the corrosion resistance of the Mg1.52Li0.24Al0.24C0.86 alloy compared to the ternary Mg1.52Li0.24Al0.24 alloy and Mg.

A review of procedures of purification and chemical modification of carbon nanotubes with bromine

ABSTRACT In this paper, bromination methods of three morphological forms of carbon nanotubes (CNT): single-walled, double-walled and multi-walled, are reviewed along with their characteristics and purification protocols using liquid bromine. Different functionalization methods of the CNT with bromine in the liquid, gas and plasma phases, using electrochemical and electrothermal method, under microwave conditions in the presence of Lewis acids or radical precursors are also discussed.

A stereogenic heteroatom-containing substituent as an inducer of chirality in the derivatives of thiophenes (mono, oligo, and poly), fullerenes C60, and multiwalled nanotubes

GRAPHICAL ABSTRACT Abstract Synthetic procedures applied recently in our laboratory for the preparation of a new thiophene, fullerene C60 and multiwalled carbon nanotube (MWCNT) derivatives functionalized with a substituent containing an achiral and/or a stereogenic heteroatom are reviewed. Polymerization reactions of selected optically active 2-(3′-thienyl)ethyl aryl(alkyl) sulfoxides and tert-butyl-[2-(3′-thienyl)ethyl]phenylphosphine oxide are also mentioned. Mechanistic and stereochemical aspects of the presented protocols are discussed.

Carbon nanotubes functionalized with sulfur, selenium, or phosphorus or substituents containing these elements

GRAPHICAL ABSTRACT ABSTRACT The preparation of multiwalled carbon nanotubes (MWCNTs) and singlewalled carbon nanotubes (SWCNTs) doped with sulfur, selenium, or phosphorus atom or functionalized with substituents containing these elements (including a stereogenic heteroatom) is presented in this mini-review. Structural studies of newly isolated derivatives based on suitably selected spectroscopic techniques are also discussed briefly. Chances for applications of obtained carbon nanotubes doped with these heteroatoms or functionalized with substituents containing these heteroatoms are also mentioned.

Li4Ge2B as a new derivative of the Mo2B5 and Li5Sn2 structure types.

Binary and multicomponent intermetallic compounds based on lithium and p-elements of Groups III-V of the Periodic Table are useful as modern electrode materials in lithium-ion batteries. However, the interactions between the components in the Li-Ge-B ternary system have not been reported. The structure of tetralithium digermanium boride, Li4Ge2B, exhibits a new structure type, in the noncentrosymmetric space group R3m, in which all the Li, Ge and B atoms occupy sites with 3m symmetry. The title structure is closely related to the Mo2B5 and Li5Sn2 structure types, which crystallize in the centrosymmetric space group R-3m. All the atoms in the title structure are coordinated by rhombic dodecahedra (coordination number = 14), similar to the atoms in related structures. According to electronic structure calculations using the tight-binding-linear muffin-tin orbital-atomic spheres approximation (TB-LMTO-ASA) method, strong covalent Ge-Ge and Ge-B interactions were established.