A versatile strategy for tuning the color of electrochemiluminescence using silica nanoparticles

Colour emission of core-shell silica-PEG nanoparticles in water is tuned with an electrochemically induced energy transfer approach. The lack of solubility problems, side electrochemical reactions involving donors and acceptors within the nanoparticle, and the possibility of using many classes of dyes in ECL applications confirm the validity of this strategy.     

An Automatic Molecular Dispenser of Chloride

The combined activity of the 1.1.1‐cryptand and of a dicopper(II) bistren cryptate complex including chloride makes the Cl^? ion be continuously and slowly delivered to the solution, without any external intervention. The 1.1.1‐cryptand slowly releases OH^? ions, according to a defined kinetics, and each OH^? ion displaces a Cl^? ion from the cryptate. Chloride displacement induces a sharp colour change from bright yellow to aquamarine and can be conveniently monitored spectrophotometrically, even in diluted solutions. The 1.1.1‐cryptand is the motor of a molecular dispenser (the dicopper(II) cryptate) delivering chloride ion automatically, from the inside of the solution.     

Cyclometalated AuIII Complexes for Cysteine Arylation in Zinc Finger Protein Domains: towards Controlled Reductive Elimination

With the aim of exploiting the use of organometallic species for the efficient modification of proteins through C-atom transfer, the gold-mediated cysteine arylation through a reductive elimination process occurring from the reaction of cyclometalated Au^III C^N complexes with a zinc finger peptide (Cys₂His₂ type) is here reported. Among the four selected Au^III cyclometalated compounds, the [Au(C^CON)Cl₂] complex featuring the 2-benzoylpyridine (C^CON) scaffold was identified as the most prone to reductive elimination and Cys arylation in buffered aqueous solution (pH 7.4) at 37 °C by high-resolution LC electrospray ionization mass spectrometry. DFT and quantum mechanics/molecular mechanics (QM/MM) studies permitted to propose a mechanism for the title reaction that is in line with the experimental results. Overall, the results provide new insights into the reactivity of cytotoxic organogold compounds with biologically important zinc finger domains and identify initial structure–activity relationships to enable Au^III-catalyzed reductive elimination in aqueous media.     

High-performance liquid chromatographic/tandem mass spectrometric identification of the phototransformation products of tebuconazole on titanium dioxide

Tebuconazole is a widely used fungicide. The formation of by-products on irradiated titanium dioxide as a photocatalyst was evaluated. Several species derived from tebuconazole degradation were identified and characterized by HPLC/MS(n). A pattern of reactions accounting for the observed intermediates is proposed. Different parallel pathways are operating (and through these pathways the transformation of the molecule proceeds), leading to a wide range of intermediate compounds. All these molecules are more hydrophylic than tebuconazole. The main steps involved are (1) the hydroxylation of the molecule with the formation of three species having [M + H](+) 324; the hydroxylation occurs on the C-1 carbon and on the aromatic ring in the two ortho-positions; (2) the cleavage of a C--C bond with the release of the tert-butyl moiety and the formation of a species having m/z 250; analogously to step 1, also on this species a further hydroxylation reaction occurs; (3) through the loss of the triazole moiety with the formation of a structure with m/z 257.     

Statistical thermodynamics models for polyatomic adsorbates: application to adsorption of n-paraffins in 5A zeolite

Experimental adsorption isotherms of five n-paraffins (ethane, propane, butane, pentane, and hexane) in 5A zeolite were described by means of a statistical thermodynamics model for linear adsorbates (MLA) developed by Ramirez-Pastor et al. (1999) and compared with the well-known multisite Langmuir model (MSL) of Nitta et al. (1984). The experimental data, obtained by different authors in a wide range of temperatures and pressures, were correlated by using an algorithm of multiple fitting. Two main conclusions were drawn from the analysis of experimental data: (i) for small molecules (ethane, propane), MLA is the more accurate model, validating the hypothesis of the linear rigid character of the adsorbate and reinforcing previous results obtained from the analysis of computational experiments developed for dimers and linear trimers; (ii) for large molecules (n-butane, n-pentane, n-hexane), the better performance of the MSL model suggests that the admolecules adsorb in a nonlinear structure. The isosteric heat of adsorption dependence on the number of carbons obtained from our study, ranging between 23.84 kJ/mol for ethane and 59.26 kJ/mol for hexane, showed a very good agreement with previous results reported in the literature, confirming the consistency of our analysis.     

(Bis(1,2,4-triazol-1-yl)methane)silver(I) phosphino complexes: structures and spectroscopic properties of mixed-ligand coordination polymers

Adducts of the ligand bis(1,2,4-triazol-1-yl)methane (tz(2)(CH(2))) of the form AgX:tz(2)(CH(2)):ER(3):MeCN (1:1:1:x) (X = NO(3), R = Ph, E = P, As, or Sb, x = 1 or 2; X = NO(2), ClO(4), O(3)SCF(3), E = P, R = Ph, x = 0, 1 or 2; X = NO(3), ClO(4), E = P, R = cy, x = 1; X = ClO(4), E = As, R = Ph, x = 2) and AgNO(3):tz(2)(CH(2)):P(o-tolyl)(3) (2:2:1) have been synthesized and characterized in the solid state and in solution by analyses, spectral (IR, far-IR, (1)H and (13)C NMR, ESI MS data) data, and conductivity measurements. In the one-dimensional polymers (characterized by X-ray studies) AgNO(3):tz(2)(CH(2)):PPh(3):CH(3)CN (1:1:1:1), AgClO(4):tz(2)(CH(2)):PPh(3):CH(3)CN (1:1:1:2), AgNO(3):tz(2)(CH(2)):AsPh(3): CH(3)CN (1:1:1:2), and AgNO(3):tz(2)(CH(2)):SbPh(3):CH(3)CN (1:1:1:2), the silver atom can be regarded as four-coordinate, the tz(2)(CH(2)) ligands behaving as bridging groups rather than chelates, with no pair of ligands being dominant, quasi-trans, in their interactions. The AgNO(3):tz(2)(CH(2)):P(o-tolyl)(3) (2:2:1) adduct is a two-dimensional polymer containing two independent silver atoms, one four-coordinated unsymmetrically by a pair of triazolyl rings, one P(o-tolyl)(3), and a unidentate nitrate and the second by a quasi-symmetrical O(2)NO chelate and a pair of equivalent triazolyl rings.     

Chloride complexation by heptapeptides: influence of C- and N-terminal sidechains and counterion

The channel-forming diglycolylated heptapeptides containing the amino acid sequence Gly-Gly-Gly-Pro-Gly-Gly-Gly have been found to complex chloride in CDCl(3). The strength of the interaction depends on the terminal alkyl groups and on chloride's countercation.