Preconcentration of thallium(III) with 2,6-bis(N-phenyl carbamoyl) pyridine on microcrystalline naphthalene prior to its trace determination in human serum spectrophotometrically

A novel, simple, sensitive and effective method has been developed for preconcentration of thallium on 2,6-bis(N-phenyl carbamoyl)pyridine-naphthalene adsorbent in the pH range 5.0-10.0, prior to its spectrophotometric determination, based on the oxidation of bromopyrogallol red at lambda = 518 nm. This method makes it possible to quantitize thallium in the range of 3.0 x 10(-9) to 1.0 x 10(-5) M, with a detection limit (S/N=3) of 1.2 x 10(-9) M. This procedure has been successfully applied to determine the ultra trace levels of thallium in the environmental and biological samples, free from the interference of some diverse ions. The precision, expressed as relative standard deviation of three measurements is better than 4.17%.     

Elucidating the structure-dependent selectivity of CuZn towards methane and ethanol in CO2 electroreduction using tailored Cu/ZnO precatalysts

Understanding the catalyst compositional and structural features that control selectivity is of uttermost importance to target desired products in chemical reactions. In this joint experimental–computational work, we leverage tailored Cu/ZnO precatalysts as a material platform to identify the intrinsic features of methane-producing and ethanol-producing CuZn catalysts in the electrochemical CO₂ reduction reaction (CO₂RR). Specifically, we find that Cu@ZnO nanocrystals, where a central Cu domain is decorated with ZnO domains, and ZnO@Cu nanocrystals, where a central ZnO domain is decorated with Cu domains, evolve into Cu@CuZn core@shell catalysts that are selective for methane (∼52%) and ethanol (∼39%), respectively. Operando X-ray absorption spectroscopy and various microscopy methods evidence that a higher degree of surface alloying along with a higher concentration of metallic Zn improve the ethanol selectivity. Density functional theory explains that the combination of electronic and tandem effects accounts for such selectivity. These findings mark a step ahead towards understanding structure–property relationships in bimetallic catalysts for the CO₂RR and their rational tuning to increase selectivity towards target products, especially alcohols.

A higher degree of surface alloying and Zn concentration boosts the selectivity towards ethanol of CuZn catalysts in CO₂ electroreduction.     

Electrothermal vaporization, part 2: surface chemistry

This review is the second of a two-part series on evaluation of vaporization and atomization processes in electrothermal vaporizers (ETV), focused specifically on surface chemistry in ETVs. Laser desorption mass spectrometry and differential scanning calorimetry are used to investigate vaporization of Mg, Ca, Sr, Ba, and Ni. Graphite, Al, and Ta were used as the vaporizer substrate material to elucidate potential pathways with regard to surface chemistry. The results presented in parts 1 and 2 of this publication series clearly illustrate the role of surface chemistry when a substrate is heated to yield atomic or molecular vapors. Depending on the attributes of the substrate material and the extent of surface modification, the surface-induced processes that ultimately define the quantity and the nature of gas phase species includes liquid–solid interactions, solid–solid interactions, catalysis, diffusion, migration, heterogeneous reactions and intercalation.     

Practical considerations when using radio frequency-only quadrupole ion guide for atmospheric pressure ionization sources with time-of-flight mass spectrometry

Construction details and performance evaluation of a radio frequency (rf)-only quadrupole ion guide for use with an electrospray ionization time-of-flight mass spectrometer is presented in this paper. Angiotensin III and cytochrome c were used in these experiments to investigate the ion transmission properties of the rf-only quadrupole for different m/z species. In addition, influence of ion kinetic energies along with the characteristic fragmentation due to collision induced dissociation (CID) were studied. These experiments demonstrate that the transmissions of different m/z ions were not only dependent on the frequency and magnitude of the rf waveform, which is similar to a high vacuum rf-only quadrupole ion guide, but also on the pressure inside the quadrupole chamber. For the pressure range tested, low m/z ions are better focused with increasing pressure. As expected, transmission of ions are subject to space charge limitations when significant numbers of ions are focused on the axis of the quadrupole. It is also observed that CID results are related to transverse motion and longitude motion of ions inside the quadrupole region. Consequently, CID is useful for fragmentation of linear peptides and it is not effective (in present configuration) for large bulky proteins. The kinetic energy of ions that enter the repelling region of the TOFMS is ultimately determined by the ensemble effect resulting from the dc bias potential of the quadrupole (the dominant factor), skimmer-2, pressure inside the quadrupole chamber, and jet expansion. While this system is tested with an ESI source, the operational principle and design criteria are directly applicable for improving other atmospheric pressure ionization sources with time-of-flight mass analyzers such as an inductively coupled plasma ion source.     

Electrocatalytic Oxidation and Determination of Nitrite at Multi‐walled Carbon Nanotubes Modified Carbon Ceramic Electrode

In the present work, the electrochemical oxidation of nitrite on carbon ceramic electrode (CCE) modified with multi‐walled carbon nanotubes (MWCNTs) was investigated. The modified electrode exhibited catalytic activity toward the electrooxidation of nitrite. Experimental parameters such as solution pH, scan rate, concentration of nitrite and nanotubes amount were studied. It was shown nitrite can be determined by differential pulse voltammetry (DPV) and hydrodynamic amperometry (HA) using the modified electrode. Under the optimized conditions the calibration plots are linear in the concentration ranges of 15‐220 and 50‐3000 μM with limit of detections of 4.74 and 35.8 μM for DPV and HA, respectively. The modified electrode was successfully applied for analysis of nitrite in spinach sample. The results were favorbly compared to those obtained by UV‐Visible spectrophotometric method. The results of the analysis suggest that the proposed method has promise for the routine determination of nitrite in the examined products.     

Salt-assisted liquid-liquid microextraction of Cr(VI) ion using an ionic liquid for preconcentration prior to its determination by flame atomic absorption spectrometry

We report on the salt-assisted liquid-liquid microextraction of cationic complexes of Cr(VI) ion using the hydrophilic ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoraborate and potassium hydrogen phosphate. This is a novel, simple, non-toxic and effective technique for sample pretreatment technique that displays large extraction efficiency and represents a new platform where Cr(VI) is complexed with 1,5-diphenylcarbazide (DPC) in sulfuric acid medium. It was applied to the extraction of Cr(VI) in the form of the Cr(VI)-DPC complex prior to its determination by flame atomic absorption spectrometry. Cr(III) ion also can be determined by this procedure after oxidation to Cr(VI). Extraction is mainly affected by the amount of water-soluble IL, the kind and quantity of inorganic salts, by pH and the concentration of DPC. Calibration plots are linear in the range from 3 to 150?μg?L^?1 of Cr(VI), and the limit of detection is 1.25?μg?L^?1. The method was successfully applied to the speciation and determination of trace levels of Cr(III) and Cr(VI) in environmental water samples containing high levels of dissolved salts or food grade salts.

High friction from a stiff polymer using microfiber arrays

High dry friction requires intimate contact between two surfaces and is generally obtained using soft materials with an elastic modulus less than 10 MPa. We demonstrate that high-friction properties similar to rubberlike materials can also be obtained using microfiber arrays constructed from a stiff thermoplastic (polypropylene, 1 GPa). The fiber arrays have a smaller true area of contact than a rubberlike material, but polypropylene's higher interfacial shear strength provides an effective friction coefficient of greater than 5 at normal loads of 8 kPa. At the pressures tested, the fiber arrays showed more than an order of magnitude increase in shear resistance compared to the bulk material. Unlike softer materials, vertical fiber arrays of stiff polymer demonstrate no measurable adhesion on smooth surfaces due to high tensile stiffness.     

1-Butyl-2-methylpipyridinium iodide ([BMPPY]I): novel ionic liquid for the synthesis of 6-hydroxy-6-(1H-indol-3-yl)indolo[2,1-b]quinazolin-12(6H)-ones under green solvent-free conditions

Research on Chemical Intermediates - In this article we reported preparation of 1-butyl-2-methylpipyridinium iodide ([BMPPY]I), as a novel ionic liquid (IL) through simple procedure. This newly...