Silver(I) and copper(I) complexes supported by fully fluorinated 1,3,5-triazapentadienyl ligands

Synthesis of the perfluorinated 1,3,5-triazapentadiene [N{(CF(3))C(C(6)F(5))N}(2)]H and the use of its conjugate base as a supporting ligand for the isolation of silver(i) and copper(i) complexes are reported. Some of the related chemistry involving [N{(C(3)F(7))C(C(6)F(5))N}(2)](-) (that has bulkier -C(3)F(7) groups on the 1,3,5-triazapentadienyl ligand backbone) is also presented. X-ray crystallographic data show a wide variety of structures ranging from intermolecular, hydrogen-bonded chain structure for [N{(CF(3))C(C(6)F(5))N}(2)]H with a twisted W-shaped N(3)C(2) core, monomeric [N{(CF(3))C(C(6)F(5))N}(2)]Ag(CN(t)Bu)(2) and [N{(C(3)F(7))C(C(6)F(5))N}(2)]Ag(CN(t)Bu)(2) where the κ(1)-bonded triazapentadienyl ligand bonding to the metal fragment via the central nitrogen atom, monomeric [N{(CF(3))C(C(6)F(5))N}(2)]Ag(PPh(3))(2) and [N{(C(3)F(7))C(C(6)F(5))N}(2)]Ag(PPh(3))(2) that feature κ(1)-bonded triazapentadienyl ligand bonding to the metal fragment via one of the terminal nitrogen atoms, to that of the monomeric [N{(CF(3))C(C(6)F(5))N}(2)]Cu(CN(t)Bu)(2) containing a κ(2)-bonded triazapentadienyl ligand and a U-shaped NCNCN ligand backbone. The isocyanide adducts show relatively high ν(CN) values in the IR spectra.     

Synthesis, characterization and fluorescent property evaluation of 1,3,5-triaryl-2-pyrazolines

A series of 1,3,5-triaryl-2-pyrazolines was synthesized by dissolving the corresponding 4-alkoxychalcones in glacial acetic acid containing a few drops of concentrated hydrochloric acid. This step was followed by the addition of (3,4-dimethylphenyl) hydrazaine hydrochloride. Finally the target compounds were precipitated by pouring the reaction mixture onto crushed ice. The structures of the synthesized compounds were established by physicochemical and spectroscopic methods. The 1,3,5-triaryl-2-pyrazolines bearing homologous alkoxy groups were found to possess fluorescence properties in the blue region of the visible spectrum when irradiated with ultraviolet radiation. The fluorescent behavior of these compounds was studied by UV-Vis and emission spectroscopy, performed at room temperature.     

A Ratiometric Fluorescent Probe for Gold and Mercury Ions

A fluorescent probe that displays a ratiometric fluorescence response towards gold and mercury ions has been devised. Emitting at a relatively longer wavelength, the conjugated form of the fluorescent dye transforms in the presence of the gold or mercury ions into a new dye, the molecular structure of which lacks the conjugation and consequently emits at a distinctly shorter wavelength.     

Electrochemical characterization of the redox couple of Fe(III)/Fe(II) mediated by grafted polymer reference electrode (GPRE)

A grafted polymer reference electrode (GPRE) (polystyrene grafted with acrylonitrile as a monomer using gamma irradiation) was fabricated as a reference electrode using cyclic voltammetry (CV). The redox process of K₃Fe(CN)₆ during CV was studied. It was found that the redox current peaks of Fe(II)/Fe(III) in 0.1 M of KCl as supporting electrolyte is given the same oxidation–reduction current as in the Ag/AgCl reference electrode, indicating a good result of GPRE and, hence, it can be used for voltammetric analysis technique. The physical properties of GPRE include good hardness, insoluble in non-aqueous electrolytes (except dimethyl formamide and chloroform), and good stability at different solvents. In addition, the sensitivity under conditions of CV is significantly dependent on the scan rate (SR) and variation in concentration. At different SRs, redox peaks of K₃Fe(CN)₆ were observed in a reversible process: Fe(II)/Fe(III). Interestingly, the redox reaction of Fe(II)/Fe(III) solution using GCE versus GPRE remains constant even after 15 cyclings. It is therefore evident that the GPRE possesses some degree of stability. Also, the new reference electrode GPRE has improved the properties of electroanalysis of CV on the working electrode GCE in reliability with the relative standard deviation.     

C-terminal amino acid residue loss for deprotonated peptide ions containing glutamic acid, aspartic acid, or serine residues at the C-terminus

Deprotonated peptides containing C-terminal glutamic acid, aspartic acid, or serine residues were studied by sustained off-resonance irradiation collision-induced dissociation (SORI-CID) in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer with ion production by electrospray ionization (ESI). Additional studies were performed by post source decay (PSD) in a matrix-assisted laser desorption ionization/time-of-flight (MALDI/TOF) mass spectrometer. This work included both model peptides synthesized in our laboratory and bioactive peptides with more complex sequences. During SORI-CID and PSD, [M - H]- and [M - 2H]2- underwent an unusual cleavage corresponding to the elimination of the C-terminal residue. Two mechanisms are proposed to occur. They involve nucleophilic attack on the carbonyl carbon of the adjacent residue by either the carboxylate group of the C-terminus or the side chain carboxylate group of C-terminal glutamic acid and aspartic acid residues. To confirm the proposed mechanisms, AAAAAD was labelled by 18O specifically on the side chain of the aspartic acid residue. For peptides that contain multiple C-terminal glutamic acid residues, each of these residues can be sequentially eliminated from the deprotonated ions; a driving force may be the formation of a very stable pyroglutamatic acid neutral. For peptides with multiple aspartic acid residues at the C-terminus, aspartic acid residue loss is not sequential. For peptides with multiple serine residues at the C-terminus, C-terminal residue loss is sequential; however, abundant loss of other neutral molecules also occurs. In addition, the presence of basic residues (arginine or lysine) in the sequence has no effect on C-terminal residue elimination in the negative ion mode.     

In vitro evaluation of potential complexation between bovine insulin and bovine serum albumin

The objective of this study was to examine the possible binding of bovine insulin (BI) with bovine serum albumin (BSA) to form a new potential diabetogenic irreversible complex protein. Several preparations of BSA and BI were prepared. Both capillary electrophoresis and spectrophotometric analysis were undertaken to test the possibility of complexation between BI and BSA. HPLC was used to test whether the potential complex of BI and BSA is reversible or irreversible. The optimum deviation between the real and calculated absorbances was observed at a BI/BSA ratio of 2. Moreover, the migration time of BI decreased substantially with increasing ratio of BI to BSA until it became almost constant at equal molar ratio of BI/BSA. While the majority of the 2:1 BI–BSA sample detached during the HPLC analysis, which confirms the reversible character of BI–BSA binding, the HPLC chromatogram also emphasizes the formation of an irreversible complexation between the two proteins. This study provides evidence of the formation of reversible and irreversible new BI–BSA complexes under physiological conditions. This highlights the importance of examining the possible diabetogenicity of BI–BSA complex in genetically susceptible people. Copyright © 2013 John Wiley & Sons, Ltd.     

Bright,NIR‐Emitting Au23 from Au25: Characterization and Applications Including Biolabeling

A novel interfacial route has been developed for the synthesis of a bright‐red‐emitting new subnanocluster, Au₂₃, by the core etching of a widely explored and more stable cluster, Au₂₅SG₁₈ (in which SG is glutathione thiolate). A slight modification of this procedure results in the formation of two other known subnanoclusters, Au₂₂ and Au₃₃. Whereas Au₂₂ and Au₂₃ are water soluble and brightly fluorescent with quantum yields of 2.5 and 1.3 %, respectively, Au₃₃ is organic soluble and less fluorescent, with a quantum yield of 0.1 %. Au₂₃ exhibits quenching of fluorescence selectively in the presence of Cu²⁺ ions and it can therefore be used as a metal‐ion sensor. Aqueous‐ to organic‐phase transfer of Au₂₃ has been carried out with fluorescence enhancement. Solvent dependency on the fluorescence of Au₂₃ before and after phase transfer has been studied extensively and the quantum yield of the cluster varies with the solvent used. The temperature response of Au₂₃ emission has been demonstrated. The inherent fluorescence of Au₂₃ was used for imaging human hepatoma cells by employing the avidin–biotin interaction.     

Oxidation of Dimethyl Sulfide in Air Using Electron-Beam Irradiation,and Enhancement of its Oxidation Via an MnO<Subscript>2</Subscript> Catalyst

The decomposition of dimethyl sulfide (DMS) at initial concentrations of 4.5–18.0 ppmv in air was studied under electron-beam (EB) irradiation. Doses to decompose 90% of input DMS were 2.5 kGy for 4.5 ppmv, 3.4 kGy for 10.6 ppmv, and 3.9 kGy for 18.0 ppmv. HCOOH, (CH₃)₂SO, and trace CH₃OH and (CH₃)₂SO₂ were produced as irradiation products in addition to CO₂ and CO. Application of an O₃ decomposition catalyst to an irradiated sample gas led to an enhancement in the oxidation of DMS and its products into CO₂ and the decomposition of O₃. For 10.6 ppmv DMS/air, the mineralization ratio increased from 41% via only EB irradiation to 100% via the combination treatment at 6.3 kGy. The yield of CO₂ to CO_x increased from 5.3 to 87.6% by combination with catalytic oxidation. This combination treatment enables the irradiation energy used to deodorize gas streams containing DMS to be reduced.     

Efficient shooting method for solving two point boundary value problems

We present an efficient shooting method for solving two point boundary value problems. The Adomian decomposition method will be utilized to obtain a series solution of the initial value problems involved. Numerical examples and comparison of the work of others will also be done.     

Generation of Coherent Extreme Ultraviolet Radiation in an Air Gas Cell with a High Power Femtosecond Laser System

Optics and Spectroscopy - High harmonic generation (HHG) in air medium is experimentally produced by using a state-of-the-art high power laser system. The harmonic orders up to 35th harmonic are...