Norharmane: old yet highly selective dual channel ratiometric fluoride and hydrogen sulfate ion sensor

Norharmane provides a simple unexplored class of anion receptor, that allows for the ratiometric selective detection of F(-) and HSO(4)(-) ions. The presence of a strong base can easily form hydrogen bonds with the acidic hydrogen bond donor moiety and the relatively strong acid can easily protonate the basic hydrogen bond acceptor moiety, which can modulate the optical response and can detect the anions efficiently with high selectivity. In view of that, it is promising to conceive the use of these systems in various sensing applications as well as in other situations, such as anion transport and purification, where the availability of cheap and easy-to-make anion receptors, would be advantageous.     

A facile method for the synthesis of copper modified amine-functionalized mesoporous zirconia and its catalytic evaluation in C-S coupling reaction

A new copper modified amine functionalized zirconia has been synthesized by a co-condensation method using zirconium butoxide and aminopropyltriethoxy-silane (APTES) in the presence of a cationic surfactant CTAB followed by impregnation of copper. Nitrogen adsorption-desorption, X-ray powder diffraction, Fourier-transform infrared spectroscopy (FT-IR), (13)C nuclear magnetic resonance (NMR), scanning electron micrography (SEM), transmittance electron micrography (TEM), thermo gravimetric analysis-differential thermal analysis (TGA-DTA), X-ray photoelectron spectroscopy (XPS) and UV-vis DRS spectroscopic tools are used to characterize the materials. FT-IR and DRS results indicated the incorporation of Cu and amino groups on the surface of zirconia. This Cu-anchored mesoporous material acts as an efficient, reusable catalyst in the aryl-sulfur coupling reaction between aryl iodide and thiophenol for the synthesis of value added diarylsulfides.     

Electronic and vibrational spectra of some rare earth trifluoromethanesulfonates crystals

Nanocrystalline ZnO powders have been synthesized by a low temperature solution combustion method. The photoluminescence (PL) spectrum of as-formed and heat treated ZnO shows strong violet (402, 421, 437, 485 nm) and weak green (520 nm) emission peaks respectively. The PL intensities of defect related emission bands decrease with calcinations temperature indicating the decrease of Zn(i) and V(o)(+) caused by the chemisorptions of oxygen. The results are correlated with the electron paramagnetic resonance (EPR) studies. Thermoluminescence (TL) glow curves of gamma irradiated ZnO nanoparticles exhibit a single broad glow peak at ～343°C. This can be attributed to the recombination of charge carriers released from the surface states associated with oxygen defects, mainly interstitial oxygen ion centers. The trapping parameters of ZnO irradiated with various γ-doses are calculated using peak shape method. It is observed that the glow peak intensity increases with increase of gamma dose without changing glow curve shape. These two characteristic properties such as TL intensity increases with gamma dose and simple glow curve structure is an indication that the synthesized ZnO nanoparticles might be used as good TL dosimeter for high temperature application.     

Convergence analysis of virtual element methods for semilinear parabolic problems on polygonal meshes

In this article, we discuss and analyze new conforming virtual element methods (VEMs) for the approximation of semilinear parabolic problems on convex polygonal meshes in two spatial dimension. The spatial discretization is based on polynomial and suitable nonpolynomial functions, and a Euler backward scheme is employed for time discretization. The discrete formulation of both the proposed schemes—semidiscrete and fully discrete (with time discretization) is discussed in detail, and the unique solvability of the resulted schemes is discussed. A priori error estimates for the proposed schemes (semidiscrete and fully discrete) in H¹‐ and L²‐norms are derived under the assumption that the source term f is Lipschitz continuous. Some numerical experiments are conducted to illustrate the performance of the proposed scheme and to confirm the theoretical convergence rates.     

Tuning Ruthenium Carbene Complexes for Selective P−H Activation through Metal-Ligand Cooperation

The use of iminophosphoryl-tethered ruthenium carbene complexes to activate secondary phosphine P−H bonds is reported. Complexes of type [(p-cymene)-RuC(SO₂Ph)(PPh₂NR)] (with R = SiMe₃ or 4-C₆H₄−NO₂) were found to exhibit different reactivities depending on the electronics of the applied phosphine and the substituent at the iminophosphoryl moiety. Hence, the electron-rich silyl-substituted complex undergoes cyclometallation or shift of the imine moiety after cooperative activation of the P−H bond across the M=C linkage, depending on the electronics of the applied phosphine. Deuteration experiments and computational studies proved that cyclometallation is initiated by the activation process at the M=C bond and triggered by the high electron density at the metal in the phosphido intermediates. Consistently, replacement of the trimethylsilyl (TMS) group by the electron-withdrawing 4-nitrophenyl substituent allowed the selective cooperative P−H activation to form stable activation products.     

Correlation of Phosphorus Adsorption with Chemical Properties of Aluminum-Based Drinking Water Treatment Residuals Collected from Various Parts of the United States

Over the past several decades, the value of drinking water treatment residuals (WTRs), a byproduct of the coagulation process during water purification, has been recognized in various environmental applications, including sustainable remediation of phosphorus (P)-enriched soils. Aluminum-based WTRs (Al-WTRs) are suitable adsorbent materials for P, which can be obtained and processed inexpensively. However, given their heterogeneous nature, it is essential to identify an easily analyzable chemical property that can predict the capability of Al-WTRs to bind P before soil amendment. To address this issue, thirteen Al-WTRs were collected from various geographical locations around the United States. The non-hazardous nature of the Al-WTRs was ascertained first. Then, their P adsorption capacities were determined, and the chemical properties likely to influence their adsorption capacities were examined. Statistical models were built to identify a single property to best predict the P adsorption capacity of the Al-WTRs. Results show that all investigated Al-WTRs are safe for environmental applications, and oxalate-extractable aluminum is a significant indicator of the P adsorption capacity of Al-WTRs (p-value = 0.0002, R² = 0.7). This study is the first to report a simple chemical test that can be easily applied to predict the efficacy of Al-WTRs in binding P before their broadscale land application.     

Phosphorus and Heavy Metals Removal from Stormwater Runoff Using Granulated Industrial Waste for Retrofitting Catch Basins

Phosphorus and heavy metals are washed off and transported with stormwater runoff to nearby surface water bodies resulting in environmental and human health risks. Catch basins remain one of the primary gateways through which stormwater runoff and pollutants from urban areas are transported. Retrofitting catch basins to enhance their phosphorus and heavy metal removal can be an effective approach. In this study, aluminum-based water treatment residual (WTR, a non-hazardous byproduct of the water treatment process) was granulated via a green method to serve as a sustainable filter material, called WTR granules, for enhancing the capabilities of catch basins to remove phosphorus and heavy metals. The WTR granules were field tested in a parking lot in Hoboken, New Jersey. Twelve storm events were monitored. The results showed that the WTR granules significantly (p < 0.05) reduced dissolved P, Cu, and Zn, as well as total P, Cu, Pb, and Zn concentrations in stormwater runoff without signs of disintegration. No flooding or water ponding was observed during the implementation. Results suggest the WTR granules are an inexpensive, green filter material that can be used for retrofitting catch basins to remove phosphorus and heavy metals effectively.     

Short peptide-based cross-β amyloids exploit dual residues for phosphoesterase like activity

Herein, we report that short peptides are capable of exploiting their anti-parallel registry to access cross-β stacks to expose more than one catalytic residue, exhibiting the traits of advanced binding pockets of enzymes. Binding pockets decorated with more than one catalytic residue facilitate substrate binding and process kinetically unfavourable chemical transformations. The solvent-exposed guanidinium and imidazole moieties on the cross-β microphases synergistically bind to polarise and hydrolyse diverse kinetically stable model substrates of nucleases and phosphatase. Mutation of either histidine or arginine results in a drastic decline in the rate of hydrolysis. These results not only support the argument of short amyloid peptides as the earliest protein folds but also suggest their interactions with nucleic acid congeners, foreshadowing the mutualistic biopolymer relationships that fueled the chemical emergence of life.

Amyloid based short peptide assemblies use antiparallel registry to expose multiple catalytic residues to bind and cleave kinetically stable phosphoester bonds of nucleic acid congeners, foreshadowing interactions of protein folds with nucleic acids.     

Effects of the Low Frequencies of Noise on On–Off Intermittency

A bifurcating system subject to multiplicative noise can exhibit on–off intermittency close to the instability threshold. For a canonical system, we discuss the dependence of this intermittency on the Power Spectrum Density (PSD) of the noise. Our study is based on the calculation of the Probability Density Function (PDF) of the unstable variable. We derive analytical results for some particular types of noises and interpret them in the framework of on-off intermittency. Besides, we perform a cumulant expansion (N. G. van Kampen, 24, 171 (1976).) for a random noise with arbitrary power spectrum density and we show that the intermittent regime is controlled by the ratio between the departure from the threshold and the value of the PSD of the noise at zero frequency. Our results are in agreement with numerical simulations performed with two types of random perturbations: colored Gaussian noise and deterministic fluctuations of a chaotic variable. Extensions of this study to another, more complex, system are presented and the underlying mechanisms are discussed. PACS Number: 05.40.-a, 05.45.-a, 91.25.-r     

Electronic absorption spectra of 1,2,3-trimethyl benzene

The electronic absorption spectra of 1,2,3-trimethyl benzene in the vapour and solid phases and in an isobutyl alcohol rigid glass at 90°K are described in this paper. Some characteristic features of the vibrational structure of the spectra are discussed.