Saw-sedge <Emphasis Type="Italic">Cladium mariscus</Emphasis> as a functional low-cost adsorbent for effective removal of 2,4-dichlorophenoxyacetic acid from aqueous systems

For the first time in the published literature, a study is described concerning the use of the saw-sedge Cladium mariscus (C. mariscus) for adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous systems. Among the experiments carried out, the elemental composition of C. mariscus was determined (C = 48.0 %, H = 7.1 %, N = 0.95 %, S = 0.4 %), FTIR spectroscopic analysis was performed to confirm the chemical structure of the adsorbent, and porous structure parameters were measured: BET surface area (A _BET  = 0.6 m²/g), total pore volume (V _p  = 0.001 cm³/g) and average pore size (S _p  = 6.6 nm). It was shown that the effectiveness of removal of 2,4-D from aqueous systems using C. mariscus depends on parameters of the process: contact time, system pH, mass of sorbent, and temperature. Maximum adsorption was attained for a solution at pH = 3. Further increase in the alkalinity of the tested systems led to a reduction in the effectiveness of the process. The kinetic of adsorption of 2,4-D by C. mariscus was also determined, and thermodynamic aspects were investigated. The experimental data obtained correspond to a pseudo-second-order kinetic model of type 1. Additionally the negative values obtained for ΔHº indicate that the process is exothermic, and the negative values of ΔGº show it to be spontaneous. As the temperature of the system increases the spontaneity of adsorption is reduced, in accordance with the exothermic nature of the process.     

Influence of electronic and steric effects on stability constants and electrochemical reversibility of divalent ion complexes with glycine and sarcosine. A glass electrode potentiometric, sampled direct current polarographic, virtual potentiometric, and molecular modelling study

Cd^II complexes with glycine (gly) and sarcosine (sar) were studied by glass electrode potentiometry, direct current polarography, virtual potentiometry, and molecular modelling. The electrochemically reversible Cd^II–glycine–OH labile system was best described by a model consisting of M(HL), ML, ML₂, ML₃, ML(OH) and ML₂(OH) (M = Cd^II, L = gly) with the overall stability constants, as log β, determined to be 10.30 ± 0.05, 4.21 ± 0.03, 7.30 ± 0.05, 9.84 ± 0.04, 8.9 ± 0.1, and 10.75 ± 0.10, respectively. In case of the electrochemically quasi-reversible Cd^II–sarcosine–OH labile system, only ML, ML₂ and ML₃ (M = Cd^II, L = sar) were found and their stability constants, as log β, were determined to be 3.80 ± 0.03, 6.91 ± 0.07, and 8.9 ± 0.4, respectively. Stability constants for the ML complexes, the prime focus of this work, were thus established with an uncertainty smaller than 0.05 log units. The observed departure from electrochemical reversibility for the Cd–sarcosine–OH system was attributed mainly to the decrease in the transfer coefficient . The MM2 force field, supplemented by additional parameters, reproduced the reported crystal structures of diaqua-bis(glycinato-O,N)nickel(II) and fac-tri(glycinato)-nickelate(II) very well. These parameters were used to predict structures of all possible isomers of (i) [Ni(H₂O)₄(gly)]⁺ and [Ni(H₂O)₄(sar)]⁺; and (ii) [Ni(H₂O)₃(IDA)] and [Ni(H₂O)₃(MIDA)] (IDA = iminodiacetic acid, MIDA = N-methyl iminodiacetic acid) by molecular mechanics/simulated annealing methods. The change in strain energy, ΔU_str, that accompanies the substitution of one ligand by another (ML + L′ → ML′ + L), was computed and a strain energy ΔU_str = +0.28 kcal mol⁻¹ for the reaction [Ni(H₂O)₄(gly)]⁺ + sar → [Ni(H₂O)₄(sar)]⁺ + gly was found. This predicts the monoglycine complex to be marginally more stable. By contrast, for the reaction [Ni(H₂O)₃IDA] + MIDA → [Ni(H₂O)₃MIDA] + IDA, ΔU_str = −0.64 kcal mol⁻¹, and the monoMIDA complex is predicted to be more stable. This correlates well with (i) stability constants for Cd–gly and Cd–sar reported here; and (ii) known stability constants of ML complex for glycine, sarcosine, IDA, and MIDA.     

Fluorescence amplification by electrochemically deposited silver nanowires with fractal architecture

Electrochemically deposited silver structures with nanowires 50-100 nm in diameter show high fluorescence amplification and strongly reduced fluorescence lifetimes. Both quantities depend on the structure thickness. With increasing thickness the fluorescence amplification proportionally increases and the fluorescence lifetime decreases. This thickness dependence is caused by fluorophore interaction with a system of plasmon excitations in coupled nanowires extending over micrometer size regions. Thus the amplification is attributed to a combination of extended structure area and strong plasmonic coupling between nanowires which also help to radiatively scatter the fluorescence emission.     

Highly Z-Selective Horner–Wadsworth–Emmons Olefination Using Modified Still–Gennari-Type Reagents

In this report, new, easily accessible reagents for highly Z-selective HWE reactions are presented. Alkyl di-(1,1,1,3,3,3-hexafluoroisopropyl)phosphonoacetates, structurally similar to Still–Gennari type reagents, were tested in HWE reactions with a series of various aldehydes. Very good Z-selectivity (up to a 98:2 Z:E ratio) was achieved in most cases along with high yields. Application of the new reagents may be a valuable, practical alternative to the well-established Still–Gennari or Ando Z-selective carbonyl group olefination protocols.     

Coordination Sites for Sodium and Potassium Ions in Nucleophilic Adeninate Contact ion-Pairs: A Molecular-Wide and Electron Density-Based (MOWED) Perspective

The adeninate anion (Ade⁻) is a useful nucleophile used in the synthesis of many prodrugs (including those for HIV AIDS treatment). It exists as a contact ion-pair (CIP) with Na⁺ and K⁺ (M⁺) but the site of coordination is not obvious from spectroscopic data. Herein, a molecular-wide and electron density-based (MOWED) computational approach implemented in the implicit solvation model showed a strong preference for bidentate ion coordination at the N3 and N9 atoms. The N3N9-CIP has (i) the strongest inter-ionic interaction, by −30 kcal mol⁻¹, with a significant (10–15%) covalent contribution, (ii) the most stabilized bonding framework for Ade⁻, and (iii) displays the largest ion-induced polarization of Ade⁻, rendering the N3 and N9 the most negative and, hence, most nucleophilic atoms. Alkylation of the adeninate anion at these two positions can therefore be readily explained when the metal coordinated complex is considered as the nucleophile. The addition of explicit DMSO solvent molecules did not change the trend in most nucleophilic N-atoms of Ade⁻ for the in-plane M-Ade complexes in M-Ade-(DMSO)₄ molecular systems. MOWED-based studies of the strength and nature of interactions between DMSO solvent molecules and counter ions and Ade⁻ revealed an interesting and unexpected chemistry of intermolecular chemical bonding.     

Resolution of multiexponential spectral relaxation of Yt-base by global analysis of collisionally quenched samples

We measured the wavelength-dependent intensity decays of 4,9-dihydro-4,6-dimethyl-9-oxo-1H-imidazo-1,2a-purine (Y_t-base) in propanol to determine the time-resolved emission spectra and rates of spectral relaxation. We found that resolution of the spectral relaxation times was dramatically improved by global analysis of the frequency-domain data with increasing amounts of the collisional quencher CCl₄. Collisional quenching preferentially decreases the longer-lived relaxed component of the emission, thereby increasing the fractional contribution of the incompletely relaxed portion of the emission. The data could not be explained by a single spectral relaxation time, and at least two relaxation times are needed to describe the time-dependent emission center of gravity of Y_t-base.Dedicated to Professor Stefan Paszyc on the occasion of his 70th birthday.     

Distance-dependent quenching of Nile Blue fluorescence byN,N-diethylaniline observed by frequency-domain fluorometry

Fluorescence quenching of Nile Blue by amines is thought to be due to electron transfer to the excited dye molecule from the amine electron donor. We used electron transfer quenching of Nile blue byN,N-diethylaniline in propylene glycol as a model system for an interaction which depends exponentially on distance. We investigated the time dependence of the presumed distance-dependent process using gigahertz harmonic-content frequency-domain fluorometry. The frequency-domain data and the steady-state quantum yield were analyzed globally based on either the Smoluchowski-Collins-Kimball radiation boundary condition (RBC) model or the distancedependent quenching (DDQ) model, in which the rate of quenching depends exponentially on the flourophore-quencher distance. We performed a global analysis which included both the frequencydomain time-resolved decays and the steady-state intensities. The latter were found to be particularly sensitive to the model and parameter values. The data cannot be satisfactorily analyzed using the RBC model for quenching. The analysis shows the excellent agreement of the DDQ model with the experimental data, supporting the applicability of the DDQ model to describe the quenching by the electron transfer process, which depends exponentially on the donor-acceptor distance.     

Dye-labeled silver nanoshell-bright particle

Silica beads with average diameters of 40-600 nm were prepared, and Ru(bpy)3(2+) complexes were incorporated into the beads. These beads were coated by silver layer by layer to generate porous but continuous metal nanoshells. The thicknesses of these metal shells were 5-50 nm. The emission band from the dyes in the silica cores was more narrow and the intensity was enhanced with growth of silver shell thickness due to coupling of the emission light from Ru(bpy)3(2+) in the cores with the metal plasmon from the silver shells. The enhancement of emission intensity was also dependent on the size of the silica core, showing that the enhancement efficiency decreased with an increase in the size of the silica beads. Lifetime measurements support the coupling mechanism between the dye and metal shell. This study can be used to develop novel dye-labeled metal particles with bright and narrow emission bands.