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.     

Stimulation of Wood Degradation by Daedaleopsis confragosa and D. tricolor

Applied Biochemistry and Biotechnology - Biological pretreatment of the lignocellulosic residues, in which white-rot fungi have a crucial role, has many advantages compared to the chemical,...     

On a chip demonstration of a functional role for Odorant Binding Protein in the preservation of olfactory receptor activity at high odorant concentration

The molecular mechanisms underlying odorant detection have been investigated using the chip based SPR technique by focusing on the dynamic interactions between transmembrane Olfactory Receptor OR1740, odorant ligands and soluble Odorant-Binding Protein (OBP-1F). The OR1740 present in the lipid bilayer of nanosomes derived from transformed yeasts specifically bound OBP-1F. The receptor preferential odorant ligand helional released bound OBP-1F from the OR-OBP complex, while unrelated odorants failed to do so. OBP-1F modified the functional OR1740 dose-response to helional, from a bell-shaped to a saturation curve, thus preserving OR activity at high ligand concentration. This unravels an active role for OBPs in olfaction, in addition to passive transport or a scavenger role. This sensorchip technology was applied to assessing native OBP-1F in a biological sample: rat olfactory mucus also displayed significant binding to OR1740 nanosomes, and the addition of helional yielded the dissociation of mucus OBP from the receptor.     

Variable neighbourhood search for colour image quantization

^** Email: nenad.mladenovic{at}brunel.ac.uk Colour image quantization is a data compression technique thatreduces the total set of colours in a digital image to a representativesubset. This problem is first expressed as a large M-medianone. The advantages of this model over the usual minimum sum-of-squaresmodel are discussed first and then, the heuristic based on variableneighbourhood search metaheuristic is applied to solve it. Computationalexperience proves that this approach compares favourably withtwo other recent state-of-the-art heuristics, based on geneticand particle swarm searches.     

ESR study of some solvent effects of the Cu(II)-aspirinate complex

Powder ESR spectra of the [Cu₂(Asp)₄](H₂O)₂ complex show the existence of Cu(II) acetate like dimers characterized by a strong antiferromagnetic exchange interaction (J=?288 cm^?1). In pyridine-dimethylformamide solutions the monomeric species prevail. Two different monomeric species, the Cu(DMF)₄ of planar-distorted tetrahedral (T_d) symmetry and the Cu(Asp)₂(DMF)₂ with elongated tetrahedral-octahedral symmetry were evidenced in DMF solution adsorbed on NaY zeolite. In 40 % Py+60 % DMF solution two monomeric species were also identified. These are Cu(Asp)₂(DMF)₂ and Cu(Asp)₂(Py)₂, the last species having a CuN₂O₂ chromophore in atrans squareplanar arrangement. In pyridine Cu(II)-aspirinate solution only the Cu(Py)₄ monomeric species of CuN₄ chromophore was evidenced.     

Interaction of Hydrogen with MOF-5

Hydrogen storage is among the most demanding challenges in the hydrogen-based energy cycle. One proposed strategy for hydrogen storage is based on physisorption on high surface area solids such as metal-organic frameworks (MOFs). Within this class of materials, MOF-5 has been the first structure studied for hydrogen storage. The IR spectroscopy of adsorbed H2 performed at 15 K and ab initio calculations show that the adsorptive properties of this material are mainly due to dispersive interactions with the internal wall structure and to weak electrostatic forces associated with O13Zn4 clusters. Calculated and measured binding enthalpies are between 2.26 and 3.5 kJ/mol, in agreement with the H2 rotational barriers reported in the literature. A minority of binding sites with higher adsorption enthalpy (7.4 kJ/mol) is also observed. These species are probably associated with OH groups on the external surfaces present as termini of the microcrystals.     

An insight into antimicrobial activity of the freshwater bryozoan Pectinatella magnifica

The antimicrobial activity of five crude extracts of the freshwater bryozoan Pectinatella magnifica (Leidy, 1851) was evaluated in vitro for the first time. P. magnifica acetone extract exhibited the highest antibacterial activity (minimum inhibitory concentrations (MIC) 0.004–0.350 mg/mL and MBC 0.007–0.500 mg/mL), while its methanol extract showed the most promising antifungal activity (MIC 0.03–0.12 mg/mL and MFC 0.06–0.25 mg/mL). Furthermore, at a concentration of 0.25 MIC, the methanol extract reduced biofilm formation of the bacterial strain Pseudomonas aeruginosa PAO1 in a considerable extent (59.14%). FTIR spectra of the most active extracts indicate the presence of carbonyl compounds, long-chain alcohols and/or sterols. According to the experimental data obtained, P. magnifica methanol extract may be considered as a good resource of novel natural products with potent antibiofilm activity against the bacterium well known for its resistance.     

Screen-printed enzymatic glucose biosensor based on a composite made from multiwalled carbon nanotubes and palladium containing particles

A composite material consisting of multiwalled carbon nanotubes and palladium containing particles was synthesized and applied to the preparation of bulk-modified screen-printed carbon electrodes (Pd-MWCNT-SPCE) and surface-modified screen-printed carbon electrodes (Pd-MWCNT/SPCE). They were characterized by cyclic voltammetry and hydrodynamic chronoamperometry in solution of pH 7.5. Both electrodes were then modified with glucose oxidase (GOx) by drop-coating a solution of GOx and Nafion® on their surface. Glucose can be determined via enzymatically formed H₂O₂. In an alternative approach, gold nanoparticles (5 nm) were incorporated into the biolayer of the electrodes. The resulting electrodes of type GOx/Pd-MWCNT-SPCE and GOx-Au/Pd-MWCNT-SPCE showed acceptable analytical performance at working potentials between ?0.20 V and ?0.50 V in case of hydrodynamic chronoamperometry. Both electrodes can be operated best at a working potential of ?0.40 V vs SCE, with acceptable linearity of the methods in sub mM concentration ranges and with LOQs of 0.14 mM and 0.07 mM for glucose for the GOx/Pd-MWCNT-SPCE and GOx-Au/Pd-MWCNT-SPCE, respectively. Incorporation of gold nanoparticles prolongs the operational lifetime of the electrodes by two weeks. The GOx/Pd-MWCNT-SPCE based method was applied to the determination of glucose in multifloral honey, and the GOx-Au/Pd-MWCNT-SPCE method to the determination of glucose in blood serum. In both cases there was a good agreement with the results obtained by commercially available equipment for determination of glucose.

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Graphical abstract Schematic of a screen printed carbon biosensor based on the use of multiwalled carbon nanotubes modified with palladium-containing particles and glucose oxidase. It can be applied to the amperometric determination of glucose in blood serum and multifloral honey