Self-Assembly of Two Isomorphous Thiocyanate Complexes of Co(II) and Ni(II) with 3-Hydroxypicolinamide

Abstract  

The synthesis, thermal and spectral characterization, and crystal structure of isomorphous thiocyanate cobalt(II) and nickel(II) complexes with 3-hydroxypicolinamide (3-OHpia), [M(C₆H₆N₂O₂)₂(NCS)₂]·2H₂O, are reported. The metal(II) ions are chelated by two cis-oriented 3-OHpia and two thiocyanate ligands in distorted octahedral geometry. The distortion within the coordination sphere is mainly imposed by formation of the chelate rings. The compounds crystallize in monoclinic space group P2/c with two symmetrically independent molecules and a = 14.4945(2) ?, b = 8.5906(1) ?, c = 16.3865(3) ?, β = 105.987(2)°, Z = 4 (1) and a = 14.4927(5) ?, b = 8.5912(3) ?, c = 16.2712(6) ?, β = 105.740(4)°, Z = 4 (2). Commonly observed supramolecular amide synthons are not robust enough to accommodate thiocyanate ions and H₂O molecules. But instead, neutral complexes are linked through hydrogen bonds leading to two different hydrogen bonding ribbon motifs involving amide moieties and H₂O molecules [C(8)R ₂²(12) along c axis] and amide moieties and thiocyanate ions [C(8)R ₂²(16) along b axis] for symmetrically related molecules labelled as 1 [Co1 (1) and Ni1 (2)] and 2 [Co2 (1) and Ni2 (2)], respectively.     

Application of flavonoids – quercetin and rutin – as new matrices for matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometric analysis of Pt(II) and Pd(II) complexes

Attempts are being made to overcome the resistance of tumour cells to platinum (Pt) drugs by the synthesis of new generations of Pt complexes, and it is important to find appropriate and simple methods for the characterization of those novel complexes. The additional applicability of such a method for the analysis of the interactions of metal complexes with biomolecules would be advantageous. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOFMS) seems to possess the capability to become this method of choice, since it could be applied to low‐mass complexes as well as for the analysis of large biomolecules. In this work the applicability of flavonoids – quercetin and rutin – as matrices for MALDI‐TOFMS analysis of dichlorido(ethylendiamine)platinum(II) ([PtCl₂(en)]), dichlorido(diaminocyclohexane)platinum(II) ([PtCl₂(dach)]) and chloride (diethylenetriamine) palladium(II) chloride ([PdCl(dien)]Cl) complexes is demonstrated. Spectra of Pt(II) and Pd(II) complexes recorded in the presence of quercetin and rutin are rather simple: Pt(II) complexes generate [M+Na]⁺ or [M+K]⁺ions, whereas the investigated Pd(II) complex gives ions generated by the loss of one Cl^? or HCl. Flavonoids give a relatively small number of well‐defined ions in the low‐mass region (at m/z 303.3 for quercetin and m/z 633.5 for rutin). Quercetin and rutin can be applied in much lower concentrations than other common MALDI matrices and require rather low laser intensity. We speculate that flavonoids stabilize the structures of the metal complexes and that they may be useful for the analysis of other biologically active metal complexes, thus implying their broader applicability. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and spectroscopic properties of furyl-phenyl-acrylates and naphthofurans and their interaction with ct- DNA

A series of novel substituted derivatives related to furyl-phenyl-acrylates and naphthofurans, was synthesized and characterized by UV/Vis and fluorescence spectroscopy. Acyclic compounds can undergo photochemical dehydrocyclization by visible light irradiation in order to obtain their cyclic derivatives. The interactions of the prepared compounds with calf thymus DNA was investigated by means of electronic absorption and fluorescence spectra. It is intriguing that addition of ct-DNA induced a fluorescence increase of acyclic derivatives, exactly the opposite of the strong fluorescence quenching observed for cyclic derivatives 10 and 12. Compound 11 showed decreasing fluorescence intensity for lower concentrations of ct-DNA, while increasing of fluorescence is observed for high excess of added ct-DNA.     

Magnesocene‐Based Electrolytes: A New Class of Electrolytes for Magnesium Batteries

Unlike ferrocene, bis(η⁵‐cyclopentadienyl)magnesium (magnesocene, MgCp₂) is slightly dissociated in solvents, such as ethers, resulting in electrolyte solutions with low conductivity. MgCp₂/tetrahydrofuran solutions make possible reversible magnesium plating and stripping with low over‐potentials for many cycles. The Mg deposits appear with a cauliflower‐like morphology. IR and NMR spectroscopy confirm that the electrolyte is stable and not decomposed during prolonged cycling. The anodic stability limit is in the range of 1.5 V (at platinum) and 1.8 V versus Mg/Mg²⁺ (at stainless steel), which may be sufficient for low‐voltage cathode materials. MgCp₂ is a first example of a completely new class of halide‐free electrolytes, which may open up a new research direction for future magnesium metal and magnesium‐ion batteries.     

Glucosinolates of Sisymbrium officinale and S. orientale

Glucosinolates (GSLs) from Sysimbrium officinale and S. orientale were analyzed qualitatively and quantitatively by their desulfo-counterparts using UHPLC-DAD-MS/MS. Eight GSLs were identified in S. officinale, including Val-derived (glucoputranjivin) and Trp-derived (4-hydroxyglucobrassicin, glucobrassicin, 4-methoxyglucobrassicin, and neoglucobrassicin) as the major ones followed by Leu-derived (Isobutyl GSL), Ile-derived (glucocochlearin) and Phe/Tyr-derived (glucosinalbin). Different S. orientale plant parts contained six GSLs, with Met-derived (progoitrin, epiprogoitrin, and gluconapin) and homoPhe-derived (gluconasturtiin) as the major ones, followed by glucosinalbin and neoglucobrassicin. GSL breakdown products obtained by hydrodistillation (HD) and microwave-assisted distillation from S. officinale, as well as isopropyl isothiocyanate, as the major volatile in both isolates, were tested for their cytotoxic activity using a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Generally, all volatile isolates showed similar activity toward the three cancer cell lines. The best activity was shown by isopropyl isothiocyanate at a concentration of 100 µg/mL after 72 h of incubation, with 53.18% for MDA-MB-231, 56.61% for A549, and 60.02% for the T24 cell line.     

Effect of Functionalized Benzene Derivatives as Potential Hole Scavengers for BiVO4 and rGO-BiVO4 Photoelectrocatalytic Hydrogen Evolution

Sustainable hydrogen production is one of the main challenges today in the transition to a green and sustainable economy. Photocatalytic hydrogen production is one of the most promising technologies, amongst which BiVO₄-based processes are highly attractive due to their suitable band gap for solar-driven processes. However, the performance of BiVO₄ alone in this role is often unsatisfactory. Herein we report the improvement of BiVO₄ performance with reduced graphene oxide (rGO) as a co-catalyst for the photoelectrochemical water splitting (PEC-WS) in the presence of simple functionalized benzene derivatives (SFBDs), i.e., phenol (PH), benzoic acid (BA), salicylic acid (SA), and 5-aminosalicylic acid (5-ASA) as potential photogenerated hole scavengers from contaminated wastewaters. Linear sweep voltammetry and chronoamperometry, along with electrochemical impedance spectroscopy were utilized to elucidate PEC-WS performance under illumination. rGO has remarkably improved the performance of BiVO₄ in this role by decreasing photogenerated charge recombination. In addition, 5-ASA greatly improved current densities. After 120 min under LED illumination, 0.53 μmol of H₂ was produced. The type and concentration of SFBDs can have significant and at times opposite effects on the PEC-WS performance of both BiVO₄ and rGO-BiVO₄.     

Continuous separation of Sr, Y and some actinides by mixed solvent anion exchange and determination of 89,90Sr, 238,239Pu and 241Am in soil and vegetation samples

Methodology for the determination of ^89,90Sr, Am and Pu isotopes in complex samples is given. Methodology is based on simultaneous isolation of Sr, Y and actinides from samples by mixed solvent anion exchange chromatography, mutual separation of ^89,90Sr and ⁹⁰Y from actinides, mutual separation of Th, Pu and Am by extraction chromatography, quantitative determination of ^89,90Sr by Cherenkov counting and quantitative determination of Pu and Am isotopes in soil and vegetation samples by alpha spectrometry. It is shown that Y and Sr can be efficiently separated from alkaline, alkaline earth and transition elements as well as from lanthanides and actinides on the column filed by strong base anion exchanger in nitrate form and 0.25?M HNO₃ in mixture of ethanol and methanol as eluent. It is also shown that Pu, Am and Th strongly binds on the mentioned column, can be separated from number of elements and easily be eluted from column by water. After elution actinides were mutually separated on TRU column and electrodeposited on stainless steel disc. Examination of conditions of electrodeposition was shown that chloride-oxalate electrolyte with addition of DTPA in presence of sodium hydrogen sulphate in cell with cooling and rotating platinum anode enables deposition of actinides within 1?h by 0.8?A?cm^?2 current density. Obtained peaks FWHM for Pu, Am and Th isotopes are between 27 and 40?keV. Scanning electron microscopy picture and ED XRF analysis of electroplated discs showed that actinide deposition is followed by iron oxide formation on disc surface. The methodology was tested by determination of ^89,90Sr, Am and Pu isotopes in ERA proficiency testing samples (low level activity samples). Obtained results shows that ^89,90Sr, ²⁴¹Am and ^238,239Pu can be simultaneously separated on anion exchange column, ^89,90Sr can be determined by Cherenkov counting with a satisfactory accuracy and limit of determination within 1?C3?days after separation. ²⁴¹Am and ^238,239Pu can easily be separated on TRU column and determined after electrodeposition with acceptable accuracy within 1?day.