Elucidating the structure-dependent photocatalytic properties of Bi2WO6: a synthesis guided investigation

Polycrystalline microspheres and single-crystalline microplates of Bi(2)WO(6) have been synthesized by ultrasonic spray pyrolysis. Herein, these materials are evaluated as photocatalysts for the visible light mediated degradation of rhodamine B, a model pollutant, and the results compared to those obtained with Bi(2)WO(6) prepared by traditional methods. The microplates, which displayed the best crystallinity and highest surface area, were anticipated to facilitate the greatest rate of dye photodegradation. However, the polycrystalline microspheres outperformed both the Bi(2)WO(6) microplates and traditional samples. To understand the origin of this result, the local and macroscale structures of the Bi(2)WO(6) samples were comprehensively characterized by spectroscopy techniques (diffuse reflectance, fluorescence, Raman, and X-ray photoelectron spectroscopy) as well as electron microscopy and diffraction. This analysis found that the enhanced performance of the Bi(2)WO(6) microspheres results from the expression of a hydrophilic surface, a low concentration of point defects, and a moderate surface area. This finding highlights the significant role synthesis plays in imparting structure and functionality to solid materials.     

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.     

Lewis Acid Mediated Vinyl‐Transfer Reaction of Alkynes to N‐Alkylimines by Using the N‐Alkyl Residue as a Sacrificial Hydrogen Donor

A variety of N‐alkyl‐α,α‐dichloroaldimines were vinylated by terminal acetylenes in the presence of Lewis acids such as In(OTf)₃ or BF₃ ? OEt₂ and hexafluoroisopropanol (HFIP) as an additive. The reaction proceeds at ambient temperature and leads to geometrically pure allylic β,β‐dichloroamines. This approach is complementary to previously reported transition‐metal‐catalyzed vinyl‐transfer methods, which are not applicable to aliphatic imines and are restricted to imines that contain an electron‐withdrawing nitrogen substituent. In the present approach, terminal alkynes were used as a source of the vinyl residue, and the N‐alkyl moiety of the imine acts as a sacrificial hydrogen donor. The additional advantage of this methodology is the fact that no external toxic or hazardous reducing agents or molecular hydrogen has to be used. This new methodology nicely combines a C(sp²)? C(sp) bond formation, hydride transfer, and an unusual cleavage of an unactivated C? N bond, thereby giving rise to functionalized primary allylic amines. A detailed experimental study supported by DFT calculations of the mechanism has been done.     

Doped Nano‐Sized Copper(I) Oxide (Cu2O) on Melamine?Formaldehyde Resin: a Highly Efficient Heterogeneous Nano Catalyst for ‘Click’ Synthesis of Some Novel 1H‐1,2,3‐Triazole Derivatives Having Antibacterial Activity

A facile and simple protocol for the 1,3‐dipolar cycloaddition of organic azides with terminal alkynes catalyzed by doped nano‐sized Cu₂O on melamine? formaldehyde resin (nano‐Cu₂O? MFR) as a new and convenient heterogeneous catalyst is described. In this method, ‘click’ cycloaddition of various structurally diverse β‐azido alcohols and alkynes in the presence of nano‐Cu₂O? MFR in H₂O/THF 1 : 2 furnished the corresponding 1,4‐disubstituted 1H‐1,2,3‐triazole adducts 1a – 1o in good to excellent yields at room temperature (Scheme and Table 3). The nano‐Cu₂O? MFR was characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD), inductively coupled plasma (ICP) analysis, and FT‐IR. The nano‐Cu₂O? MFR could be easily recovered and recycled from the reaction mixture and reused for many consecutive trials without significant decrease in activity (Table 4). The in vitro antibacterial activities of all synthesized compounds were tested on several Gram‐positive and/or Gram‐negative bacteria (Table 5). The results demonstrate the promising antibacterial activity for some of the synthesized compounds.     

Using magnetic core‐shell nanoparticles coated with an ionic liquid dispersion assisted by effervescence powder for the micro‐solid‐phase extraction of four beta blockers from human plasma by ultra high performance liquid chromatography with mass spectrometry detection

In this work, a novel, efficient, and green sorbent, SiO₂@Fe₃O₄ has been created and functionalized with 1‐butyl‐3‐methylimidazolium hexafluorophosphate as an ionic liquid. This sorbent was applied for microextraction of four beta blockers, propranolol, metoprolol, atenolol, and alprenolol with bupivacaine as internal standard from human plasma followed by liquid chromatography with mass spectrometric detection. A mixture of sodium bicarbonate and sodium dihydrogen phosphate was used as an extractant dispersive agent (effervescent power) to enhance the interaction between the magnetic sorbent and analytes. Main affecting parameters on microextraction and elution were optimized. Figures of merit for dispersive solid phase extraction with ionic liquid coated magnetic nanoparticles assisted by effervescent powder were calculated under the optimized conditions. The detection limits for propranolol, metoprolol, atenolol, and alprenolol were found at 0.33, 0.62, 0.03, and 0.44 ng/mL, respectively. For all analytes, good linearity was obtained. Intra‐ (n = 5) and interday (n = 10) precision were both under 6.3% while the preconcentration factors were obtained in the range between 15–18. The extraction efficiencies for each analyte ranged from 75 to 91%. The method was successfully applied for determination of trace amounts of the beta blockers in human plasma samples.     

Screening for exogenous androgen anabolic steroids in human hair by liquid chromatography/orbitrap-high resolution mass spectrometry

A method for the screening of various anabolic steroids and their esters in human hair, based on liquid-chromatography–high resolution mass spectrometry using an Exactive benchtop Orbitrap mass spectrometer, has been set up and validated. This method involved methanolic incubation of 30 mg of hair and analysis of the relevant extract in HPLC using a C18 column. The mass detector, with nominal resolving power of 100,000, operated in full scan mode in APCI under positive ionization mode. Analytes were identified by exact mass, correspondence of isotopic cluster and retention times.     

Effect of a cocatalyst modifier in the synthesis of ultrahigh molecular weight polyethylene having reduced number of entanglements

The use of a hindered phenol to trap free trimethylaluminum (TMA) in methylaluminoxane (MAO) solutions has been reported to improve the performance of single‐site, homogeneous catalysts for olefin polymerization. In the present study, with the help of rheological analyses, we have investigated and compared the molecular weight, molecular weight distribution and entanglement density of ultrahigh molecular weight polyethylene synthesized with a single‐site catalyst activated by MAO and phenol‐modified MAO. While the number average molecular weight (M_n) of the obtained polymers remains the same for both activations, a higher yield and a higher entanglement density are found in the initial stages of polymerization on using phenol‐modified MAO as the cocatalyst. These results suggest that on using the phenol‐modified MAO as activator, a higher number of active sites are obtained. Surprisingly in the presence of untreated MAO, a tail in the higher molecular mass region is produced. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013     

Imidazolinone herbicides in strongly acidic media: Speciation and electroreduction

From UV-visible measurements and potentiometric titrations it follows that the lowest pK values (pK₁) of imidazolinone herbicides correspond to the simultaneous protonation/dissociation equilibria of both the pyridinic (or quinolinic) nitrogen and the carboxyl group, the following pK (pK₂) to the imminium nitrogen and the basic pK (pK₃) to the dissociation of the imido nitrogen. Below pH 6 and down to pH c.a. 2.5, the dominant form of the herbicide is a double ion having both positive and negative charges, this being important in discussing the effect of pH in the natural dynamics of imidazolinone herbicides, especially in their soil sorption. Electrochemical studies of the reduction of the herbicides were made on mercury and carbon electrodes in strongly acidic media (0.1 to 2.7 M H₂SO₄) as well up to pH 7. The reduction signals were all attributed to the reduction of the imidazolinone ring except the second peak/wave that was found to have originated by the reduction of the pyridine/quinoline ring. A signal observed in strongly acidic media and at highly negative overpotentials was attributed to the reduction of the imidazolinone ring of the product of the previous reduction in a process consisting of two reversible electron transfers followed by a protonation reaction.     

Elucidating the nature and reactivity of Ti ions incorporated in the framework of AlPO-5 molecular sieves. New evidence from 31P HYSCORE spectroscopy

The incorporation of Ti ions within the framework of aluminophosphate zeotype AlPO-5 and their chemical reactivity is studied by means of CW-EPR, HYSCORE, and UV-vis spectroscopies. Upon reduction, Ti(3+) ions are formed, which exhibit large (31)P hyperfine couplings, providing direct evidence for framework substitution of reducible Ti ions at Al sites.     

Some thoughts on electrospray ionization mechanisms

Electrospray ionization (ESI) mechanisms are highly complex, due to a series of physical and chemical phenomena taking place on a complex system, as a solution is. In fact, even if the solution of an analyte in a protic medium can be considered at first sight to be a two-component system, the presence of solvent dissociation equilibria and the possible interactions solvent-solvent dissociation products, solvent dissociation products-analyte make this system highly complex, also for the presence of possible ionic compounds (for example, Na(+), K(+)) which strongly affect the above equilibria. A high number of research articles have been published, mainly devoted to charged droplet production and to gas-phase ion generation. They all show the high complexity of the processes affecting electrospray measurements related to either the chemical equilibria present in the condensed phase and to electrolysis processes at the emitter tip or to the processes occurring in the sprayed droplets. As a result, the chemical composition inside the small droplets from which the analyte ions are generated can be significantly different from those in sprayed solution. In this review, after a short survey of the proposed ESI mechanisms, some experiments are described. They were performed to examine if ion mobility in solution, before the formation of the sprayed charged droplets, can affect the ESI results. The data, obtained by studying both inorganic and organic analytes, indicate that the ESI spectra are dependent on the analyte dimension and charge state which, as a consequence, affect their ion mobility in solution.