A series of gallium(III) and iron(III) complexes with five different 4N-substituted alpha-N-heterocyclic thiosemicarbazones, viz., 2-acetylpyridine N,N-dimethylthiosemicarbazone (1), 2-acetylpyridine N-pyrrolidinylthiosemicarbazone (2), acetylpyrazine N,N-dimethylthiosemicarbazone (3), acetylpyrazine N-pyrrolidinylthiosemicarbazone (4), and acetylpyrazine N-piperidinylthiosemicarbazone (5), with the general formula [GaLCl2] (HL = 1 and 2) and [ML2][Y] (M = Ga, HL = 1-5, Y = PF6; M = Fe, HL = 1-5, Y = FeCl4 and PF6) were synthesized and characterized by elemental analysis, a number of spectroscopic methods (NMR, IR, UV-vis), mass spectrometry, and X-ray crystallography. The in vitro antitumor potency was studied in two human cancer cell lines (41M and SK-BR-3). The central metal ions exert pronounced effects in a divergent manner: gallium(III) enhances, whereas iron(III) weakens the cytotoxicity of the ligands. The capacity of ligand 1 and its Ga(III) and Fe(III) complexes to destroy the tyrosyl radical of the presumed target ribonucleotide reductase is reported.

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High contents of chlorine and alkalies restrict the use of biomass in energy production. Alkali chlorides vaporize during combustion. Chlorine tends to produce corrosive deposits and unacceptably high emissions of HCl and dioxins. Chlorine recovery and enrichment of Cl, Na, K, Ca, Al, and Si in coarse and fine fly ash were studied experimentally with two electrically stabilized bubbling fluidized bed (BFB) reactors capable of reproducing the particle residence times existing in full-scale BFB plants. Feedstocks were fir (mixture of heartwood and bark), paper sludge, and blends of fir with agricultural waste or plastic waste. Sulfur concentrations of feed components were low (<0.5 wt %), while chlorine and potassium concentrations ranged widely (0.02−3.2 wt % for Cl and 0.07−3.1 wt % for K). Aluminum-containing additives (kaolin, bauxite and fly ash from a pulverized coal plant) and limestone were added to the feedstocks at various dosages to evaluate their influence on Cl behavior and enrichment of the elements of interest. HCl was measured by FTIR and wet-absorption methods. Different ash samples (bed, cyclone and filter ash) were characterized for their Cl content and the major ash-forming constituents. Cl was completely volatilized from bed ash and recovered only in coarse (cyclone) and fine (filter) fly ash fractions. Al-containing additives increased HCl formation and decreased Cl concentration in the fly ash. In the case of Al−Si based additives, evidence was found of the formation of alkali aluminum silicates from alkali chlorides. The aluminum silicates were transferred mainly to the coarse fly ash fraction. Al-based additives also seemed to liberate Cl from alkali chlorides with reactions forming water-soluble alkali compounds. Limestone had the opposite effect to the Al-containing additives by binding Cl from gas phase to fly ash, but mainly to the coarse fly ash fraction. The results will be useful in optimizing the behavior of chlorine in bubbling bed combustion of Cl- and alkali-containing biomass.