Microwave-accelerated ring-opening polymerization (ROP) of cyclic esters catalyzed by ionic liquid (IL) anions, intercalated into layered double hydroxides (LDHs), has been recently described as a fast and environmentally friendly synthetic way to prepare biodegradable polyester/LDH nanocomposites. However, to observe this synergistic catalytic effect between microwaves and IL anions and to achieve a homogeneous structure of the final polymer nanocomposite, the IL anions must be efficiently intercalated inside the LDH structure. Herein, we investigate the effects of various metal compositions of M2+/Al3+ LDHs (M = Mg, Co, and Ca) and different LDH synthetic routes (one-step direct coprecipitation, two-step coprecipitation/anion exchange, and two-step urea/anion exchange) on the intercalation efficiency of trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate IL. The most effective IL anion intercalation was observed for Ca2+/Al3+ LDH prepared using the two-step method consisting of coprecipitation and subsequent anion exchange. After optimization, this synthetic pathway led to the production of LDHs with intercalated IL anions and a reduced amount of intercalated water (<0.6 wt %). The catalytic ability of thus optimized LDH particles was demonstrated on the microwave-assisted ROP of ε-caprolactone, showing rapid progress of polymerization. Within minutes, the polycaprolactones with an average molecular mass in the range of 20 000-50 000 g/mol containing fully delaminated and exfoliated LDH nanoparticles were obtained.
- Publikační typ
- časopisecké články MeSH
Cytotoxic complexes containing molybdenum are widely studied as a potential substitution for commercially used drugs that often suffer from pronounced side effects and cellular resistance. Compounds of the type [(η5 -Cp')Mo(CO)2 (N,N L)][BF4 ], where Cp is cyclopentadienyl and N,N L is a bidentate ligand, are well known for their strong anticancer activity. It is a generally accepted paradigm that the nature of the coordinated N,N L ligand has a major impact on the cytotoxicity. In this study, a series of new functionalised Cp complexes of molybdenum was synthesised from derivatised fulvenes as π-ligand precursors. Indeed, the coordination sphere's modulation by various N,N-chelating ligands afforded species active toward leukemic cell line MOLT-4 with IC50 values depending on the character of the N,N-chelator used. However, following study clearly showed that functionalisation of the Cp ring with an amine moiety considerably improved cytotoxicity. These results are of crucial importance for the future design of highly active cytotoxic drugs, as modification of cyclopentadienyl is believed to have a minor effect on biological activity.
- Klíčová slova
- MOLT-4, antitumor agents, cyclopentadienyl ligand, cytotoxicity, fulvene,
- MeSH
- buněčné linie MeSH
- cyklopentany chemie farmakologie MeSH
- komplexní sloučeniny chemická syntéza chemie farmakologie MeSH
- lidé MeSH
- ligandy MeSH
- molekulární struktura MeSH
- molybden chemie farmakologie MeSH
- proliferace buněk účinky léků MeSH
- protinádorové látky chemická syntéza chemie farmakologie MeSH
- screeningové testy protinádorových léčiv MeSH
- vztah mezi dávkou a účinkem léčiva MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Názvy látek
- cyklopentany MeSH
- komplexní sloučeniny MeSH
- ligandy MeSH
- molybden MeSH
- protinádorové látky MeSH
The reactivity of two lithium amides derived from bis-(2-pyridyl)amine (dpa)H or its methyl-substituted congener bis-(6-methyl-2-pyridyl)amine (Me-dpa)H, i.e. (dpa)Li (1) and (Me-dpa)Li (2), toward ECl2 (where E = Ge (dioxane complex) and Sn) is reported. This study produced both heteroleptic complexes (dpa)GeCl (3), [(dpa)SnCl]2 (4), and (Me-dpa)GeCl (5) and homoleptic complexes (dpa)2E (E = Ge (6) or Sn (7)) and (Me-dpa)2E (E = Ge (8) or Sn (9)). The structures of all complexes were established by single-crystal X-ray diffraction analysis showing significant differences depending on the E atom and ligand used. By contrast, in solution, the majority of compounds showed a fluxional behaviour as demonstrated by the NMR study. Finally, it turned out that the Me-dpa ligand, unlike dpa, is able to form ate complexes [(Me-dpa)3E]Li (E = Ge (10), Sn (11) or Pb (12)), whose structures were determined by single-crystal X-ray diffraction analysis. This study revealed the formation of two isomers for Ge and Sn complexes depending on the coordination preference of the lithium atom being coordinated either by nitrogen donors (10-12) or solely by the Ge or Sn electron lone pair (10a and 11a). Furthermore, the NMR experiments proved that the germanium complex 10 exhibits only limited stability in solution and decomposes to germylene 8 and lithium amide 2.
- Publikační typ
- časopisecké články MeSH
The carbon nanomaterials and congeners, e.g., graphene or graphene oxide (GO), dispose of numerous unique properties, which are not necessarily intrinsic but might be related to a content of impurities. The oxidation step of GO synthesis introduces a considerable amount of metallic species. Therefore, large-scale purification is an actual scientific challenge. Here we describe new purification technique (salt‑washing), which is based on three consecutive steps: (a) aggregation of GO sheets with NaCl (b) washing of the aggregates and (c) removing of the salt to afford purified GO (swGO). The considerably improved purity of swGO was demonstrated by ICP and EPR spectroscopy. The microscopic methods (TEM with SEAD, AFM) proved that the salt-washing does not affect the morphology or concentration of defects, showing the aggregation of GO with NaCl is fully reversible. The eligibility of swGO for biomedical applications was tested using fibroblastic cell cultures. The determined IC50 values clearly show a strong correlation between the purity of samples and cytotoxicity. Although the purification decreases cytotoxicity of GO, the IC50 values are still low proving that cytotoxic effect is not only impurities-related but also an intrinsic property. These findings may represent a serious limitation for usage of GO in biomedical applications.
- Klíčová slova
- Cytotoxicity, Graphene oxide, HDF, MRC-5 cell cultures, Purification, Salt-washing,
- MeSH
- chlorid sodný toxicita MeSH
- grafit * toxicita MeSH
- nanostruktury * MeSH
- oxidace-redukce MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- chlorid sodný MeSH
- grafit * MeSH
- graphene oxide MeSH Prohlížeč
We report herein a new class of mixed propene-indenyl complexes of molybdenum and tungsten stabilized by a strong N→M intramolecular coordination. The complexes [{η5:κN-1-(C9H6N)C9H6}(η2-C3H6)M(CO)2][BF4] (M = Mo, W) were obtained in nearly quantitative yields by the protonation of the η3-allyl ligand in compounds [(η3-C3H5){η5-1-(C9H6N)C9H6}M(CO)2] (M = Mo, W). In contrast to known η2-alkene molybdenum and tungsten compounds, the species presented here are easily isolated in the solid state. The tungsten compound [{η5:κN-1-(C9H6N)C9H6}(η2-C3H6)W(CO)2][BF4] is stable at room temperature, and its structure was unambiguously confirmed by X-ray diffraction. The reactivity of both propene complexes toward several monodentate donors was examined. In the case of dimethyl sulfide, ligand exchange takes place to afford [{η5:κN-1-(C9H6N)C9H6}M(CO)2(SMe2)][BF4] (M = Mo, W) while acetonitrile induces η5→η3 haptotropic rearrangement to give [{η3:κN-1-(C9H6N)C9H6}M(CO)2(NCMe)2][BF4] (M = Mo, W).
- Publikační typ
- časopisecké články MeSH
A series of six indenyl molybdenum compounds bearing a thiophenyl function in the side chain were prepared and characterized by analytical and spectroscopic methods. The structures of [(η5-C9H6CH2C4H3S)(η3-C3H5)Mo(CO)2] and [(η5-C9H6CH2C4H3S)Mo(CO)2(bpy)][BF4] were determined by single-crystal X-ray diffraction. The compounds bearing N,N-chelating ligands exhibit increased cytotoxic activity against human leukemia cell lines MOLT-4; up to two orders of magnitude lower IC50 values were observed compared to analogues with unsubstituted indenyl, which clearly demonstrates the strong effect of the indenyl ligand modification on the biological activity of the molybdenum(ii) compounds. The highest cytostatic potential was observed for the complex bearing 4,7-diphenyl-1,10-phenanthtoline [(η5-C9H6CH2C4H3S)Mo(CO)2(Ph2phen)][BF4] with IC50 (MOLT-4) = 0.19 ± 0.02 μM. Detailed regulation of the molecular and cellular mechanism by this derivative was investigated on the lung carcinoma cell line A549 and compared with the lung fibroblast cell line MRC-5. Rather unusual differences in the effects on tumor and non-tumor cell lines provide a unique insight into the cytostatic action of molybdenum(ii) complexes.
- Publikační typ
- časopisecké články MeSH
