Oxidation of highly unstable <4 nm diameter gold nanoparticles 850 mV negative of the bulk oxidation potential

Here we describe the oxidation of <4 nm diameter Au nanoparticles (NPs) attached to indium tin oxide-coated glass electrodes in Br(-) and Cl(-) solution. Borohydride reduction of AuCl(4)(-) in the presence of hexanethiol or trisodium citrate (15 min) led to Au NPs <4 nm in diameter. After electrochemical and ozone removal of the hexanthiolate ligands from the thiol-coated Au NPs, Au oxidation peaks appeared in the range 0-400 mV vs Ag/AgCl (1 M KCl), which is 850-450 mV negative of the bulk Au oxidation peak near 850 mV. The oxidation potential of citrate-coated Au NPs is in the 300-500 mV range and those of 4 and 12 nm diameter Au NPs in the 660-780 mV range. The large negative shift in potential agrees with theory for NPs in the 1-2 nm diameter range. The oxidation potential of Au in Cl(-) solution is positive of that in Br(-) solution, but the difference decreases dramatically as the NP size decreases, showing less dependence on the halide for smaller NPs.     

Synthesis and functionalization of magnetite nanoparticles with different amino-functional alkoxysilanes

Superparamagnetic iron oxide (SPIO) nanoparticles show great promise for many biotechnological applications. This paper addresses the synthesis and characterization of SPIO nanoparticles grafted with three different alkoxysilanes: 3-aminopropyl-triethoxysilane (APTES), 3-aminopropyl-ethyl-diethoxysilane (APDES) and 3-aminopropyl-diethy-ethoxysilane (APES). SPIO nanoparticles with an average particle diameter of 10 nm were prepared by chemical sonoprecipitation. As confirmed by Fourier transform infrared (FTIR) spectroscopy, silylation of these nanoparticles occurs through a two-step process. Decreasing the number of alkoxide groups reduced the concentration of free amino groups on the SPIO surface ([SPIO-NH₂]—APTES>APDES>APES). This phenomenon results from steric contributions and the formation of H-bonded amines provided by the ethyl groups present in the APDES and APES molecules. A simulation of SPIO nanoparticles in a saline physiologic solution shows that the ethyl groups impart larger steric stability onto the ferrofluids, which reduces aggregation. The magnetization (M) versus magnetic field (H) curves show that the synthesized iron oxide nanoparticles display superparamagnetic behavior. The zero-field cooling (ZFC) and field cooling (FC) curves show that the changes in the blocking temperature depend on the alkoxysilane-functionalized particle surface.     

Envelopes of commutative rings

Given a significative class ℱ of commutative rings, we study the precise conditions under which a commutative ring R has an ℱ-envelope. A full answer is obtained when ℱ is the class of fields, semisimple commutative rings or integral domains. When ℱ is the class of Noetherian rings, we give a full answer when the Krull dimension of R is zero and when the envelope is required to be epimorphic. The general problem is reduced to identifying the class of non-Noetherian rings having a monomorphic Noetherian envelope, which we conjecture is the empty class.     

Modular system for studying tonal sound excitation in resonators with heat addition and mean flow

An educational experimental system has been developed for studying tonal sound generation in acoustic resonators. Tones are excited by either heat addition or vortex shedding in the presence of mean flow. The system construction is straightforward and inexpensive. Several test arrangements and experimental data are described in this paper. The experimental setups include a modified Rijke tube, a standing-wave thermoacoustic engine, a baffled tube with mean flow, and an acoustic energy harvester with a piezoelement. Simplified mathematical models for interpreting data are discussed, and references are provided to literature with more advanced analyses. The developed system can assist both graduate and undergraduate students in understanding acoustic instabilities via conducting and analyzing interesting experiments.     

Medium-sized rings versus macrocycles through rhodium-catalyzed ring-expansion reactions of cyclic acetals

α-Diazo β-ketoesters and diketones react with cyclic acetals under Rh(II) catalysis to yield unprecedented polyoxygenated 8- and 9-membered rings in one pot. The reactions occur under mild conditions with yields up to 90%. A perfect regioselectivity is obtained, which can be rationalized through a mechanistic hypothesis that considers 1) the formation of an oxonium ylide, 2) its transformation into an unsaturated acyclic oxocarbenium electrophilic intermediate, and 3) an intramolecular nucleophilic attack in a direct application of Baldwin's rules.     

Reversible solvatomagnetic switching in a spongelike manganese(II)-copper(II) 3D open framework with a pillared square/octagonal layer architecture

The concept of "molecular magnetic sponges" was introduced for the first time in 1999 by the creative imagination of the late Olivier Kahn. It refers to the exotic spongelike behavior of certain molecule-based materials that undergo a dramatic change of their magnetic properties upon reversible dehydration/rehydration processes. Here we report a unique example of a manganese(II)-copper(II) mixed-metal-organic framework of formula [Na(H(2)O)(4)](4)[Mn(4){Cu(2)(mpba)(2)(H(2)O)(4)}(3)]·56.5H(2)O (1) (mpba=N,N'-1,3-phenylenebis(oxamate)). Compound 1 possesses a 3D Mn(II)(4)Cu(II)(6) pillared layer structure with mixed square and octagonal pores of approximate dimensions 1.2×1.2 nm and 2.1×3.0 nm, respectively, hosting a large amount of crystallization H(2)O molecules and hydrated Na(I) countercations as guests. It reversibly switches from a crystalline hydrated phase with long-range ferromagnetic ordering at a rather high critical temperature (T(c)) of 22.5 K to an amorphous dehydrated phase with T(c) as low as 2.3 K, which is accompanied by a breathing-type dynamic effect involving a large crystal volume (ca. 45%) and color changes after water desorption/adsorption. The combination of both the open-framework structure and the spongelike optical, mechanical, and magnetic switching behavior in this new class of oxamato-based porous magnets offers fascinating possibilities in designing multifunctional materials for host-guest molecular sensing.     

Optimization of matrix solid-phase dispersion conditions for organic fungicides determination in soil samples

A simplified sample preparation method, based on the matrix solid-phase dispersion technique, is proposed for the sensitive determination of 15 organic fungicides in vineyard soils by gas chromatography-mass spectrometry (GC-MS). Under final working conditions, sieved samples (0.5 g) were blended and dispersed with 2 g of C18 and transferred to a polypropylene syringe containing 1 g of diatomaceous earth. Analytes were recovered using 10 mL of ethyl acetate, this extract was concentrated to 1 mL and fungicides determined by GC-MS, without additional cleanup. The method provided recoveries in the range from 74 to 122% for soils with total carbon contents up to 5.5% and it allowed the use of external standard as quantification technique. Inter-day precision, given as relative standard deviations, stayed between 3 and 13%, and the limits of quantification were comprised between 0.6 and 15 ng g(-1). Several fungicides were found in the top layer of vineyard soils with the highest detection frequency and maximum concentration corresponding to iprovalicarb. Some real samples were also submitted to pressurized liquid extraction. Measured concentrations were in excellent agreement with those obtained by matrix solid-phase dispersion, which reinforces the accuracy of the latter methodology.     

Hollow‐fiber liquid‐phase microextraction and gas chromatography‐mass spectrometry of barbiturates in whole blood samples

Here, we present a method for measuring barbiturates (butalbital, secobarbital, pentobarbital, and phenobarbital) in whole blood samples. To accomplish these measurements, analytes were extracted by means of hollow‐fiber liquid‐phase microextraction in the three‐phase mode. Hollow‐fiber pores were filled with decanol, and a solution of sodium hydroxide (pH 13) was introduced into the lumen of the fiber (acceptor phase). The fiber was submersed in the acidified blood sample, and the system was subjected to an ultrasonic bath. After a 5 min extraction, the acceptor phase was withdrawn from the fiber and dried under a nitrogen stream. The residue was reconstituted with ethyl acetate and trimethylanilinium hydroxide. An aliquot of 1.0 μL of this solution was injected into the gas chromatograph/mass spectrometer, with the derivatization reaction occurring in the hot injector port (flash methylation). The method proved to be simple and rapid, and only a small amount of organic solvent (decanol) was needed for extraction. The detection limit was 0.5 μg/mL for all the analyzed barbiturates. The calibration curves were linear over the specified range (1.0 to 10.0 μg/mL). This method was successfully applied to postmortem samples (heart blood and femoral blood) collected from three deceased persons previously exposed to barbiturates.     

Reaction of β-blockers and β-agonist pharmaceuticals with aqueous chlorine. Investigation of kinetics and by-products by liquid chromatography quadrupole time-of-flight mass spectrometry

The degradation of two β-blockers (atenolol and propranolol) and one β-receptor agonist (salbutamol) during water chlorination was investigated by liquid chromatography-mass spectrometry (LC-MS). An accurate-mass quadrupole time-of-flight system (QTOF) was used to follow the time course of the pharmaceuticals and also used in the identification of the by-products. The degradation kinetics of these drugs was investigated at different concentrations of chlorine, bromide and sample pH by means of a Box-Behnken experimental design. Depending on these factors, dissipation half-lives varied in the ranges 68-145 h for atenolol, 1.3-33 min for salbutamol and 42-8362 min for propranolol. Normally, an increase in chlorine dosage and pH resulted in faster degradation of these pharmaceuticals. Moreover, the presence of bromide in water samples also resulted in a faster transformation of atenolol at low chlorine doses. The use of an accurate-mass high-resolution LC-QTOF-MS system permitted the identification of a total of 14 by-products. The transformation pathway of β-blockers/agonists consisted mainly of halogenations, hydroxylations and dealkylations. Also, many of these by-products are stable, depending on the chlorination operational parameters employed.