Study of Langmuir and Langmuir-Blodgett films of odorant-binding protein/amphiphile for odorant biosensors

To make ultrathin films for the fabrication of artificial olfactory systems, odorant biosensors, we have investigated mixed Langmuir and Langmuir-Blodgett films of odorant-binding protein/amphiphile. Under optimized experimental conditions (phosphate buffer solution, pH 7.5, OBP-1F concentration of 4 mg L(-1), target pressure 35 mN m(-1)), the mixed monolayer at the air/water interface is very stable and has been efficiently transferred onto gold supports, which were previously functionalized by self-assembled monolayers (SAMs) with 1-octadecanethiol (ODT). Atomic force microscopy and electrochemical impedance spectroscopy were used to characterize mixed Langmuir-Blodgett (LB) films before and after contact with a specific odorant molecule, isoamyl acetate. AFM phase images show a higher contrast after contact with the odorant molecule due to the new structure of the OBP-1F/ODA LB film. Non-Faradaic electrochemical spectroscopy (EIS) is used to quantify the effect of the odorant based on the electrical properties of the OBP-1F/ODA LB film, as its resistance strongly decreases from 1.18 MOmega (before contact) to 25 kOmega (after contact).     

Multiresidue determination of pesticides in drinking and related waters by gas chromatography/mass spectrometry after solid-phase extraction: interlaboratory study

As part of a project funded by the European Commission (EC) for the development and evaluation of multiresidue methods for analysis of drinking and related waters, 15 European laboratories evaluated a method using styrene-divinylbenzene co-polymer solid-phase extraction followed by gas chromatography/mass spectrometry. The main aim of the study was to evaluate whether the method meets the requirements of EC Directive 98/83 in terms of accuracy, precision, and detection limit for 22 pesticides according to the following requirements: limit of detection, < or = 0.025 microg/L; accuracy, expressed as recovery between 75 and 125%; and precision, expressed as repeatability relative standard deviation of the method of < 12.5% and as reproducibility relative standard deviation of the method of < 25%. Analyses for unknown concentrations were performed with fortified commercial bottled and tap waters. All laboratories were able to achieve detection limits of 0.01 microg/L for all pesticides except dimethoate and desisopropylatrazine (0.02 microg/L). The criteria for repeatability were met for all compounds except trifluralin, dimethoate, and lindane in bottled water and chlorpyrifos, dimethoate, and lindane in tap water. The criteria for reproducibility were met for all compounds except trifluralin, dimethoate, and lindane in bottled water and pendimethalin, chlorpyrifos, dimethoate, terbutryn, and lindane in tap water. In terms of accuracy, the method meets the requirements for all pesticides in both matrixes, except for lindane in bottled water and lindane and chlorpyrifos in tap water.     

Novel pyrimidine-bridged platinum(II) complexes: multinuclear magnetic resonance spectroscopy and crystal structures of (NR4)2[(PtCl3)2(mu-pyrimidine)] and cis- and trans-[Pt(R2SO)Cl2]2(mu-pyrimidine)

Two new types of pyrimidine-bridged Pt(II) complexes, (NR4)2[(PtCl3)2(mu-pm)] and cis- and trans-[Pt(R2SO)Cl2]2(mu-pm) where pm = pyrimidine, were synthesized and characterized by IR and multinuclear magnetic resonance spectroscopies and by crystallographic methods. Compounds with dimethylsulfoxide, tetramethylenesulfoxide, di-n-propylsulfoxide (DPrSO), di-n-butylsulfoxide (DBuSO), dibenzylsulfoxide (DBzSO), and diphenylsulfoxide were studied. The aqueous reaction of K2PtCl4 with pyrimidine produced the [(PtCl3)2(mu-pm)](2-) ions, which can be precipitated with a NR4(+) salt. The aqueous reaction of K[Pt(R2SO)Cl3] with pyrimidine in a 2:1 ratio produced the dinuclear species trans-[Pt(R2SO)Cl2]2(mu-pm). With DBuSO and DBzSO, the analogous cis isomers were also obtained. The 195Pt NMR resonances of the trans dimeric complexes were observed at higher field (av -3088 ppm) than the cis compounds (av -2948 ppm). The 195Pt coupling constants with the atoms of pyrimidine 3J(195Pt-1H) and 3J(195Pt-13C) are larger in the cis configuration than in the trans analogues. The crystal structures of two ionic complexes, (NR4)2[(PtCl3)2(mu-pm)] (R = Me and n-Bu), and of three mixed-ligands dimers, trans-[Pt(R2SO)Cl2]2(mu-pm) (R2SO = DMSO, DPrSO) and cis-Pt(DBuSO)Cl2]2(mu-pm), were determined.     

Rapid access to 3-(N-substituted)-aminoquinolin-2(1H)-ones using palladium-catalyzed C-N bond coupling reaction

A series of 3-(N-substituted)-aminoquinolin-2(1H)-ones have been synthesized by the palladium-catalyzed C-N coupling reaction starting from 3-bromoquinolin-2-(1H)-ones. Various nucleophiles including amines, amides, sulfonamides, carbamates and ureas have been used successfully. In all the cases, the reactions take place rapidly in 1,4-dioxane and proceed in good to excellent yield using palladium acetate as a catalyst, Xantphos as a ligand and Cs₂CO₃ as a base.     

Two-stage Off-Gel isoelectric focusing: protein followed by peptide fractionation and application to proteome analysis of human plasma

This paper presents the recently introduced Off-Gel electrophoresis (OGE) technology as a versatile tool to reproducibly fractionate intact proteins and peptides into discrete liquid fractions. The coupling of two stages of OGE, i.e., the separation of intact proteins in a first-stage followed by fractionation of peptides derived from each protein fraction after proteolysis in a second stage, results in an array of 15 x 15 fractions that are directly amenable to additional peptide fractionation like reverse-phase liquid chromatography (RPC). The analysis of all second-stage peptide fractions from only the first-stage protein fraction representing pH 5.0 -5.15 by on-line reverse-phase LC-tandem mass spectrometry resulted in the identification of 53 proteins (337 peptides), of which 10 were on different immunoglobulin (Ig) chains, with an input of only 1.5 mg human blood plasma proteins. Increasing the protein load to approximately 12 mg increased the number of identified proteins in the same protein fraction to 73 proteins (449 peptides), of which 15 were Ig-related. Immunodepletion of six of the most abundant proteins (albumin, transferrin, haptoglobin, IgG, IgA, and alpha-1-antitrypsin) prior to first-stage OGE with an input of 1.5 mg of protein (equivalent to approximately 10 mg nondepleted plasma) resulted in the identification of 81 proteins (660 peptides), of which three were still Ig fragments. The pI-based separation of peptides appears to be nonuniform based on the theoretically determined pI values of identified peptides. This observation specifically accounts for the neutral zone (pI 5-8) and can be accounted for by the physicochemical properties of the peptides given by their amino acid composition. The power of OGE separation of proteins and peptides is discussed with a focus on the use of the knowledge about the pI of proteins and peptides that assist the validation of correct identifications together with the retention time of peptides on RPC.     

A study of the thermal and light induced spin transition in [FeL2](BF4)2 and [FeL2](ClO4)2 L=2,6-di(3-methylpyrazol-1-yl)pyrazine

The spin crossover compounds [FeL2](BF4)2, L=2,6-di(3-methylpyrazol-1-yl)pyrazine and [FeL2](ClO4)2 have very unusual two stage spin transitions which are initially steep and then become more gradual. A detailed variable temperature single crystal X-ray diffraction study has shown that the course of the spin transition is controlled by an order-disorder transition in the counter anions. The high and low spin states both crystallise in the tetragonal space group I4, the structures of the high and low spin states are presented at 290 and 30 K, respectively. The title compounds are shown to undergo LIESST (Light Induced Excited Spin State Trapping) under irradiation with either red or green laser light with wavelengths of 632.8 and 532.06 nm, respectively, at 30 K. The cell parameters for the tetragonal photo-induced metastable high spin state at this temperature are a= 9.169(6), c= 17.77(1) A for [FeL2](ClO4)2 with an increase in unit cell volume of 21 A3, and a= 9.11(1), c= 17.75(2) A and an increase in volume of 42.8 A3 for [FeL2](BF4)2.     

Synthesis and characterization of Mo(6) chalcobromides and cyano-substituted compounds built from a novel [(Mo(6)Br(i)(6)Y(i)(2))L(a)(6)](n)()(-) discrete cluster unit (Y(i) = S or Se and L(a) = Br or CN)

The syntheses, crystal structures determined by single-crystal X-ray diffraction, and characterizations of new Mo(6) cluster chalcobromides and cyano-substituted compounds with 24 valence electrons per Mo(6) cluster (VEC = 24), are presented in this work. The structures of Cs(4)Mo(6)Br(12)S(2) and Cs(4)Mo(6)Br(12)Se(2) prepared by solid state routes are based on the novel [(Mo(6)Br(i)(6)Y(i)(2))Br(a)(6)](4)(-) (Y = S, Se) discrete units in which two chalcogen and six bromine ligands randomly occupy the inner positions, while the six apical ones are fully occupied by bromine atoms. The interaction of these two compounds with aqueous KCN solution results in apical ligand exchange giving the two first Mo(6) cyano-chalcohalides: Cs(0.4)K(0.6)(Et(4)N)(11)[(Mo(6)Br(6)S(2))(CN)(6)](3).16H(2)O and Cs(0.4)K(0.6)(Et(4)N)(11)[(Mo(6)Br(6)Se(2))(CN)(6)](3).16H(2)O. Their crystal structures, built from the original [(Mo(6)Br(i)(6)Y(i)(2))(CN)(a)(6)](4)(-) discrete units, will be compared to those of the two solid state precursors and other previously reported Mo(6) cluster compounds. Their redox properties and (77)Se NMR characterizations will be presented. Crystal data: Cs(4)Mo(6)Br(12)S(2), orthorhombic, Pbca (No. 61), a = 11.511(5) A, b = 18.772(5) A, c = 28.381 A (5), Z = 8; Cs(4)Mo(6)Br(12)Se(2), Pbca (No. 61), a = 11.6237(1) A, b = 18.9447(1) A, c = 28.4874(1) A, Z = 8; Cs(0.4)K(0.6)(Et(4)N)(11)[(Mo(6)Br(6)S(2))(CN)(6)](3).16H(2)O, Pm-3m (No. 221), a = 17.1969(4) A, Z = 1; Cs(0.4)K(0.6)(Et(4)N)(11)[(Mo(6)Br(6)Se(2))(CN)(6)](3).16H(2)O, Pm-3m (No. 221), a = 17.235(5) A, Z = 1.     

A Density Functional Theory Study on Electronic Structure and Second—order Nonlinear Optical Properties of Some Push—Pull Molecules

Time-dependent density-functional theory(TDDFT)has been applied to calculate the electronic structure and second-order nonlinear optical(NLO) properties of some organic molecules.The two-dimensional(2-D)charge transfer charateristics of calculated molecules were studied and compared with corresponding experimental results.All the theoretical results agree well with the measurement.For 2-D molecule with two-fold symmetry,the dominant charge transfer is off-diagonal,while for three-fold symmetry 2-D molecule,the dominant charge transfer is not only between branches and central group but also among branches.     

New benzyne approach to the synthesis of dehydroaporphines, 4,5-dioxoaporphines and aristolactams

A new strategy for the synthesis of some aporphinoid alkaloids is described. It is based on the intermolecular Diels-Alder cyclization between benzyne and an appropriate methylene isoquinoline derivative.     

Triplex and quadruplex DNA structures studied by electrospray mass spectrometry

DNA triplex and quadruplex structures have been successfully detected by electrospray ionization mass spectrometry (ESI-MS). Circular dichroism and UV-melting experiments show that these structures are stable in 150 mM ammonium acetate at pH 7 for the quadruplexes and pH 5.5 for the triplexes. The studied quadruplexes were the tetramer [d(TGGGGT)](4), the dimer [d(GGGGTTTTGGGG)](2), and the intramolecular folded strand dGGG(TTAGGG)(3), which is an analog of the human telomeric sequence. The absence of sodium contamination allowed demonstration of the specific inclusion of n - 1 ammonium cations in the quadruplex structures, where n is the number of consecutive G-tetrads. We also detected the complexes between the quadruplexes and the quadruplex-specific drug mesoporphyrin IX. MS/MS spectra of [d(TGGGGT)](4) and the complex with the drug are also reported. As the drug does not displace the ammonium cations, one can conclude that the drug binds at the exterior of the tetrads, and not between them. For the triplex structure the ESI-MS spectra show the detection of the specific triplex, at m/z values typically higher than those typically observed for duplex species. Upon MS/MS the antigene strand, which is bound into the major groove of the duplex, separates from the triplex. This is the same dissociation pathway as in solution. To our knowledge this is the first report of a triplex DNA structure by electrospray mass spectrometry.