Preparation of sinapinaldehyde modified mesoporous silica materials and their application in selective extraction of trace Pb(II)

A new solid phase extractant, sinapinaldehyde (SA) modified SBA-15 mesoporous silica, was developed for selective extraction and preconcentration of trace Pb(II) from aqueous solutions. The successful immobilization of SA on SBA-15 and the strong interaction between SA-SBA-15 and Pb(II) were characterized and confirmed by FTIR spectroscopy and scanning electron microscopy. Parameters such as solution pH, shaking time, eluent condition and sample volume were optimized so that the maximum removal of Pb(II) from solution could be achieved. At pH 4.0, the maximum adsorption capacity of the sorbent for Pb(II) was found to be 33.6?mg?g^?1 and the adsorbed Pb(II) could be completely eluted using a mixed solution of 2?M HCl and 5% CS(NH₂)₂. Some common metal ions such as K(I), Na(I), Mg(II), Ca(II), Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) did not interfere with the adsorption of trace Pb(II). The detection limit of the present method was found to be 1.3?ng?mL^?1 and the relative standard deviation was less than 2.0% (n?=?8). These results suggested that this new sorbent is very efficient and selective for the removal of trace Pb(II) in water samples.     

Influence of Gold Nanoparticle Film Porosity on the Chemiresistive Sensing Performance

The porosity of 1‐hexanethiol‐functionalised gold nanoparticle films was assessed and utilised as chemiresistor sensors. Electrochemical capacitance measurements showed that the accessibility of electrolytes of different ionic strengths into the pores depended on the thickness of the electric double layer formed. A large variation in capacitance was measured in 0.01–1000 mM NaClO₄, implying a wide pore size distribution. The change in morphology of the nanoparticle films upon storage in air, water and ethanol for two weeks was investigated. There was a significant decrease in the electrochemical capacitance at high electrolyte concentrations for the ethanol‐stored films compared to the freshly‐prepared films suggesting a decrease in the number of small pores of radii in the range of 0.3–3 nm. This was further supported by optical topographical measurements where a decrease in the thickness of ethanol‐stored films was observed relative to the freshly‐prepared films. The porous nature of the nanoparticle films was found to have an effect on the chemical sensing behaviour. When used as chemiresistor sensors, for the detection of heptane in water, the ethanol‐stored films provided larger resistance changes and longer response times. This suggests that the more densely packed ethanol‐stored films provided more sites that enabled film swelling, and that diffusion of the analyte occurred through the narrower water‐filled pores. This demonstrates the effect of different storage conditions on film morphology and subsequently sensor response.     

ELECTRON-TRANSFER PROCESSES. PART 40. REACTION OF ALKYL RADICALS WITH DIPHENYLPHOSPHIDE ANION

Abstract

The anion Ph₂P^? (K⁺, 18-crown-6) reacts with t-BuHgCl in HMPA to form Ph₂PCMe₃ by a free radical chain mechanism. In Me₂SO, Ph₂P(O)CMe₃ is produced. Reaction of Ph₂P^? with PhCOCH₂HgCl yields the oxidative dimerization product isolable from HMPA but readily converted to Ph₂P(O)P(O)Ph₂ in Me₂SO.     

Preparation of N-Arylated Heterocycles by Nucleophilic Aromatic Substitution

Nucleophilic aromatic substitution of fluorobenzoates and fluorophenylnitriles with weakly basic heterocycles readily occur. This synthetic methodology is utillized to produce potent angiotensin-II antagonists.     

Single‐pulse pulsed laser polymerization–electron paramagnetic resonance investigations into the termination kinetics of n‐butyl acrylate macromonomers

The termination of model mid‐chain radicals (MCRs), which mimic radicals that occur in acrylate polymerization over a broad range of reaction conditions, has been studied by single‐pulse pulsed laser polymerization (SP‐PLP) in conjunction with electron paramagnetic resonance spectroscopy. The model radicals were generated by initiator‐fragment addition to acrylic macromonomers that were preformed prior to the kinetic experiments, thus enabling separation of termination from the propagation reaction, for these model radicals propagate sparingly, if at all, on the timescale of SP‐PLP experiments. Termination rate coefficients of the MCRs were determined in the temperature range of 0–60°C in acetonitrile and butyl propionate solution as well as in bulk macromonomer over the range of 0–100 °C. Termination rate coefficients slightly below those of the corresponding secondary radicals were deduced, demonstrating the relatively high termination activity of this species, even when undergoing MCR–MCR termination. For chain length of 10, a reduction by a factor of 6 is observed. Unusually high activation energies were found for the termination rate coefficient in these systems, with 35 kJ mol^?1 being determined for bulk macromonomer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Controlled Synthesis of Large Single Crystals of Metal-Organic Framework CPO-27-Ni Prepared by a Modulation Approach: In situ Single-Crystal X-ray Diffraction Studies

The size of single crystals of the metal-organic framework CPO-27-Ni was incrementally increased through a series of modulated syntheses. A novel linker modulated synthesis using 2,5-dihydroxyterephthalic acid and the isomeric ligand 4,6-dihydroxyisophthalic acid yielded large single crystals of CPO-27-Ni (∼70 μm). All materials were shown to have high crystallinity and phase purity through powder X-ray diffraction, electron microscopy methods, thermogravimetry, and compositional analysis. For the first time single-crystal structure analyses were carried out on CPO-27-Ni. High BET surface areas and nitric oxide (NO) release efficiencies were recorded for all materials. Large single crystals of CPO-27-Ni showed a prolonged NO release and proved suitable for in situ single-crystal diffraction experiments to follow the NO adsorption. An efficient activation protocol was developed, leading to a dehydrated structure after just 4 h, which subsequently was NO-loaded, leading to a first NO loaded single-crystal structural model of CPO-27-Ni.     

Two-stage financial risk tolerance assessment using data envelopment analysis

Typical questionnaires administered by financial advisors to assess financial risk tolerance mostly contain stereotypes of people, have seemingly unscientific scoring approaches and often treat risk as a one-dimensional concept. In this work, a mathematical tool was developed to assess relative risk tolerance using Data Envelopment Analysis (DEA). At its core, it is a novel questionnaire that characterizes risk by its four distinct elements: propensity, attitude, capacity, and knowledge. Over 180 individuals were surveyed and their responses were analyzed using the Slacks-based measure type of DEA efficiency model. Results show that the multidimensionality of risk must be considered for complete assessment of risk tolerance. This approach also provides insight into the relationship between risk, its elements and other variables. Specifically, the perception of risk varies by gender as men are generally less risk averse than women. In fact, risk attitude and knowledge scores are consistently lower for women, while there is no statistical difference in their risk capacity and propensity compared to men. The tool can also serve as a “risk calculator” for an appropriate and defensible method to meet legal compliance requirements, known as the “Know Your Client” rule, that exist for Canadian financial institutions and their advisors.