A Layer‐by‐Layer Film of Chitosan in a Taste Sensor Application

Chitosan is alternated with sulfonated polystyrene (PSS) to build layer‐by‐layer (LBL) films that are used as sensing units in an electronic tongue. Using impedance spectroscopy as the principle method of detection, an array using chitosan/PSS LBL film and a bare gold electrode as the sensing units was capable of distinguishing the basic tastes – salty, sweet, bitter, and sour – to a concentration below the human threshold. The suitability of chitosan as a sensing material was confirmed by using this sensor to distinguish red wines according to their vintage, vineyard, and brands.

PCA Plot for red wine samples obtained from impedance measurements at 1 kHz for the sensor array comprising a 3‐bilayer chitosan/PSS film and a bare gold electrode.     

Metal ions in biological systems, vol. 2, metal ligand complexes : ed. by H. Sigel, Dekker, New York, 1973, xiv + 294 pages, $25.25

The kinetic isotope effect for β-hydride elimination from alkyliridium(I) complexes has bee found to be k_H/k_D = 2.28 ± 0.20.     

Bimetallic reactivity. One-site addition two-metal oxidation reaction of dioxygen with a bimetallic dicobalt(II) complex bearing five- and six-coordinate sites

The di-Co(2+) complex, [Co(2+)(mu-OH)(oxapyme)Co(2+)(H(2)O)](+), contains an unsymmetrical binucleating ligand (oxapyme) which provides five- and six-coordinate metal sites when a hydroxide bridge is introduced. This complex absorbs 1 equiv of O(2) irreversibly in solution, producing an unstable di-Co(3+) oxygenated product. The oxygenated product has been studied at low temperatures, where its electronic absorption and (1)H NMR spectra were recorded. It is probable that the oxygenation reaction involves a one-site addition two-metal oxidation reaction to produce an end-on-bonded peroxide ligand at the available coordination site, giving the complex [Co(3+)(mu-OH)(oxapyme)Co(3+)(mu(1)-O(2))](+). Addition of 1 equiv of HClO(4) to this oxygenation product gives a stable peroxide complex, [Co(3+)(mu,eta(1):eta(2)-O(2))(oxapyme)Co(3+)](2+), where one of the oxygen atoms bridges the two metals and is sideways bonded to one of the metals. The formation of this stable complex involves expulsion of the OH(-) bridge. Addition of NO(2)(-) to the sideways-bonded peroxide complex leads to the formation of another stable complex, [Co(3+)(mu,eta(1):eta(1)-O(2))(oxapyme)Co(3+)(NO(2))](+), where the peroxide forms a classic di-end-on bridge to the two metals. Both of these complexes have been fully characterized. Addition of acid to this second stable dioxygen complex leads to the release of HNO(2) and the formation of the mu,eta(1):eta(2) sideways-bonded peroxide complex.     

Probing charge-transfer processes in helium nanodroplets by optically selected mass spectrometry (OSMS): charge steering by long-range interactions

Electron impact ionization of a helium atom in a helium nanodroplet is followed by rapid charge migration, which can ultimately result in the localization of the charge on an atomic or molecular solute. This process is studied here for the cases of hydrogen cyanide, acetylene, and cyanoacetylene in helium, using a new experimental method we call optically selected mass spectrometry (OSMS). The method combines infrared laser spectroscopy with mass spectrometry to separate the contributions to the overall droplet beam mass spectrum from the various species present under a given set of conditions. This is done by vibrationally exciting a specific species that exists in a subset of the droplets (for example, the droplets containing a single HCN molecule). The resulting helium evaporation leads to a concomitant reduction in the ionization cross sections for these droplets. This method is used to study the charge migration in helium and reveals that the probability of charge transfer to a solvated molecule does not approach unity for small droplets and depends on the identity of the solvated molecule. The experimental results are explained quantitatively by considering the effect of the electrostatic potential (between the charge and the embedded molecule) on the trajectory of the migrating charge.     

Isobutane chemical ionization mass spectra of unsaturated alcohols

Analysis of the isobutane chemical ionization mass spectra of hexenols, cyclohexenols and various syn/anti pairs of bicyclic and tricyclic homoallylic alcohols shows that: (i) the spectra of the allylic alcohols are dominated by [M + H – H₂O]⁺ and [M + C₄H₉–H₂O]⁺ ions and contain traces of [M + H]⁺ ions; (ii) [M + H]⁺ ions are prominent in the spectra of acyclic and certain cyclic homoallylic alcohols; and (iii) [M + H]⁺ ions dominate the spectra of other acyclic unsaturated alcohols. The [M + H]⁺ ions may result from either: (a) protonation of the hydroxyl group, followed by a very rapid intramolecular proton transfer from the protonated hydroxyl group to the carbon–carbon double bond or internal solvation of the protonated hydroxyl group by the carbon–carbon double bond; and/or (b) direct protonation of the carbon–carbon double bond with significant internal solvation of the resulting carbocation by the hydroxyl group, which may lead to carbon–oxygen bond formation to give a protonated cyclic ether. The consequences of placing various geometric constraints on the possible intramolecular interactions between the hydroxyl group and the carbon–carbon double bond in unsaturated alcohols are explored.     

Preparation and electrochemical behavior of dimeric complexes of Ru2(III12, III12) and Ru2(IV,IV) formed by oxidative dimerization of [RuIII(edta)OH2]−

Electrochemical or chemical oxidation of [Ru^III(edta)OH₂]^? proceeds in successive half- and one-electron steps to yield dimeric complexes of Ru(III$\text{1}\text{2}$) and Ru(IV) believed to contain oxo- or dihydroxo-bridging ligands. Spectral and electrochemical properties of the complexes prepared by oxidative dimerization are described and compared with previous reports of dioxygen and peroxo complexes of Ru^III(edta). The dimeric Ru^IV(edta) complex is shown to exhibit modest activity as a catalyst for the oxidation of water to dioxygen.     

Five- and Six-Coordinate 2-Methyl-2-propanethiolato Complexes of Zirconium(IV): Synthesis and Structures of [Li(DME)(3)][Zr(SCMe(3))(5)] and [(THF)Li](2)Zr(SCMe(3))(6)

Five-coordinate and six-coordinate 2-methyl-2-propanethiolato complexes of zirconium, [Li(DME)(3)][Zr(SCMe(3))(5)] (1) and [(THF)Li](2)Zr(SCMe(3))(6) (2), were obtained from the ZrCl(4)/LiSCMe(3) reaction system. The control of the Zr coordination number, by the ether ligands, THF or DME, bound to Li, is demonstrated by the conversion of 2 into 1 upon dissolution in DME. 1 and 2 were crystallographically characterized. The structures are extensively disordered. Crystal data follow: 1, hexagonal P6(3)/m, a = b = 12.496(3) ?, c = 17.561(9) ?, Z = 2, V = 2375(1) ?(3), R = 5.0%, R(w) = 6.8%; 2, trigonal R32, a = b = 11.813(3) ?, c = 28.37(1) ?, Z = 3, V = 3428(1) ?(3), R = 5.2%, R(w) = 6.4%.     

Simultaneous quantification of terpenelactones and flavonol aglycones in hydrolyzed ginkgo biloba extract by liquid chromatography with inline ultraviolet and evaporative light scattering detection

We report here a liquid chromatography (LC) method with inline ultraviolet/evaporative light scattering (UV/ELS) detection for the simultaneous quantification of the terpenelactones and flavonol aglycones in a single sample of hydrolyzed Ginkgo biloba extract (GBE). The sample is hydrolyzed by a rapid and convenient oven heating method for 1 h at 90 degrees C with 10% hydrochloric acid. The 1 h hydrolysis was found to be equivalent to the 2.25 h reflux treatment for dry powder extract, where total flavonol glycosides were 28.4 and 28.1%, respectively. Acceptable precision was achieved for total terpenelactones [relative standard deviation (RSD) = 4.8%] by ELS detection, and total flavonol aglycones (RSD = 2.3%) by UV detection. The analytical range was 1.5 to 7.3% (w/w) for the individual terpenelactones (ELS) and 2.5 to 15.0% (w/w) for the individual glycosides (UV) calculated from the aglycones quercetin, kaempferol, and isorhamnetin. This improved method allows for the first time high throughput sample preparation coupled with the quantification of the predominant compounds generally used for quality control of GBE in a single assay.     

Investigation of bovine ubiquitin conformers separated by high-field asymmetric waveform ion mobility spectrometry: Cross section measurements using energy-loss experiments with a triple quadrupole mass spectrometer

High-field asymmetric waveform ion mobility spectrometry (FAIMS) was used to separate gas-phase conformers of bovine ubiquitin produced by electrospray ionization. These conformers were sampled by a triple quadrupole mass spectrometer where energy-loss experiments, following the work of Douglas and co-workers, were used to determine their cross sections. The measured cross sections for some conformers were readily altered by the voltages applied to the interface ion optics, therefore very gentle mass spectrometer interface conditions were required to preserve gas-phase conformers separated by FAIMS. Cross sections for 19 conformers (charge states +5 through +13) were measured. Two conformers for the +12 charge state, which were readily separated in FAIMS, were found to have similar cross sections. Based on a method to calibrate the collision gas thickness, the cross sections measured using the FAIMS/energy-loss method were compared with literature values determined using drift tube ion mobility spectrometry. The comparison illustrated that the conformers of bovine ubiquitin that were identified using drift tube ion mobility spectrometry were also observed using the FAIMS device.     

Synthesis of a selective estrogen receptor β-modulator via asymmetric phase-transfer catalysis

An efficient asymmetric synthesis of selective estrogen receptor β-modulator (S)-4-bromo-9a-butyl-8-chloro-6-fluoro-7-hydroxy-1,2,9,9a-tetrahydro-fluoren-3-one was developed. The route features a chemoselective aromatic chlorination reaction, an asymmetric phase-transfer-catalyzed alkylation of an indanone with efficient ee upgrade by racemate crystallization, and a robust bromination reaction using imidazole as an in situ bromine trap to avoid overreaction. The synthesis proceeds in 34% yield over 8 steps from 2-fluoroanisole, and provides material with >99.5% ee.