The far infrared spectrum of trans-formic acid: An extension up to 175 cm−1

The far infrared spectrum of HCOOH was recorded at a high resolution (0.0009 cm^?1) and long path length (72 m) at the far-infrared beamline, Canadian Light Source. Spectra were recorded in the region 62–300 cm^?1, showing transitions from the trans-isomer.Ground state rotational transitions with K_a up to 30, were identified up to 175 cm^?1, extending the observation reported in the literature. A total of 3321 transitions were assigned and fitted together with previous (4149) published data. An improved set of rotational parameters was obtained adopting the symmetric top (A) reduction of the rotational Hamiltonian in the I^r representation. The newly measured far infrared transitions allowed the determination of all diagonal and off diagonal 8th order parameters L and of some of the diagonal 10th order parameters P.     

Quantification of L‐ergothioneine in whole blood by hydrophilic interaction ultra‐performance liquid chromatography and UV‐detection

A new hydrophilic interaction ultra‐performance LC method was established for the whole blood measurement of L‐ergothioneine. Chromatographic separation was achieved in a fairly short time, less than 4 min, on a 100 × 2.1 mm Acquity UPLC BEH HILIC 1.7 μm column with a mobile phase consisting of a mixture of 100 mmol/L ammonium acetate/ACN/water (5:85:10, v/v/v) that flowed isocratically at 0.250 mL/min. The LOD and the limit of quantification were 3.85 and 11.67 μmol/L, respectively. The method exhibited linearity in a concentration range of 15.63–1000 μmol/L (R² > 0.999). Mean recovery was 96.34% whereas intraassay and interassay precision were 1.52 and 1.82% RSD, respectively. On the whole, the developed method is simple, fast, precise, accurate, and sensitive and may be useful for routine analyses.     

Protective Properties of Novel S‐Acyl‐Glutathione Thioesters Against Ultraviolet‐induced Oxidative Stress

UV‐induced toxicity is characterized by marked oxidative stress, accompanied by the depletion of key cellular antioxidants, particularly glutathione (GSH). Replenishing cellular GSH may represent a means of counteracting UV‐induced toxicity: however, treatment with free GSH is not therapeutically effective due to its unfavorable pharmacokinetic properties. In this study, we show that S‐acyl‐glutathione (acyl‐SG) derivatives, which consist of an acyl chain (of variable length and saturation) linked via a thioester bond to GSH, increase intracellular levels of reduced GSH in primary skin fibroblasts, adenocarcinoma HeLa and neuroblastoma SH‐SY5Y cells. Consistent with this, acyl‐SG derivatives protect against UV‐induced reactive oxygen species (ROS) production and UV‐B/C‐mediated lipid peroxidation and caspase‐3 activation in the analyzed cell lines, with unsaturated thioesters displaying a significantly greater protective effect. Taken together, our findings suggest that acyl‐SG thioesters may be therapeutically effective in the treatment of UV‐related skin disorders and oxidative stress‐mediated conditions in general.     

Unexpected high ordering of a [60]Fullerene nitroxide in the nematic phase of 4-4′-azoxyanisole

A nitroxide [60]fullerene adduct containing a pyrrolidine-1-oxyl group has been synthesized. Its orientational order in the nematic phase of the liquid crystal solvent 4,4′-azoxyanisole (PAA) has been measured from the variation of the EPR spectral parameters on passing from the isotropic to the nematic phase. Highly resolved EPR lines allow for precise evaluation of the shifts of the g, a _N and a _H values. Since the g and the hyperfine tensors are known, the order matrix could be obtained. This is compared with the one calculated with a theoretical model based on short range solute-solvent interactions, which predicts a considerable degree of orientation of the molecular axes, despite the almost spherical shape of the molecule. The agreement with experimental findings is quite good and it is further improved if a bent structure of the pyrrolidine ring is taken into account.     

Growth and Atomic-Scale Characterization of Ultrathin Silica and Germania Films: The Crucial Role of the Metal Support

The present review reports on the preparation and atomic-scale characterization of the thinnest possible films of the glass-forming materials silica and germania. To this end state-of-the-art surface science techniques, in particular scanning probe microscopy, and density functional theory calculations have been employed. The investigated films range from monolayer to bilayer coverage where both, the crystalline and the amorphous films, contain characteristic XO₄ (X=Si,Ge) building blocks. A side-by-side comparison of silica and germania monolayer, zigzag phase and bilayer films supported on Mo(112), Ru(0001), Pt(111), and Au(111) leads to a more general comprehension of the network structure of glass former materials. This allows us to understand the crucial role of the metal support for the pathway from crystalline to amorphous ultrathin film growth.     

The use of nonendcapped C18 columns in the cleanup of clenbuterol and a new adrenergic agonist from bovine liver by gas chromatography-tandem mass spectrometry analysis

More specific official methodology is needed to survey the illegal use of clenbuterol in animal production plus the synthesis of new compounds that currently elude routine analytical methods. The identification of a new adrenergic agonist, N1-(2-(4-amino-3,5-dichlorophenyl)-2-hydroxyethyl)-N1-isopropyl-propanamide (known as compound A) in animal feed has prompted studies to verify if the existing cleanup procedures developed for clenbuterol are really effective. This study considers the ion-exchange mechanism on cyanopropyl (CN), sulfonic cation exchange (SCX), mixed phase (MPH) (C8 + SCX), and nonendcapped C18 (C18NE) solid-phase extraction (SPE) columns. Results indicate that compound A (by contrast with clenbuterol) is not efficiently retained on the CN, SCX, and MPH SPE columns (recovery <10%). This finding thus leads to the development of a gas chromatography-tandem mass spectrometry procedure based on C18NE SPE that is able to purify both agonists from bovine livers spiked at 0.5, 1.0, and 2.0 ppb with a mean recovery of 93% for clenbuterol and 92% for compound A.     

Effect of ethanol on micellization and on decarboxylation of 6-nitrobenzisoxazole-3-carboxylate in aqueous cationic micelles

The effects of ethanol on the critical micellar concentration (cmc) and the rates of decarboxylation of 6-nitrobenzisoxazole-3-carboxylate (6-NBIC) have been investigated in aqueous cationic surfactants of the cetyltrialkylammonium family with bromide [CT(R)ABr], chloride [CT(R)ACl], and nitrate [CT(R)ANO3] counterions, and methyl (CTAX), n-propyl (CTPAX), and n-butyl (CTBAX) as the head group alkyl moieties. Effects upon cmc and reactivity are similar, featuring a break at the ethanol mole fraction, x(EtOH), of ca. 0.055; these effects have been related to changes in solvent structure, with formation of a clathrate at x(EtOH) = 0.055. Rate data in CTBABr were further investigated and fitting of raw kinetic data to the pseudophase model is possible up to x(EtOH) = 0.1, showing an unexpected decrease of rate constant values in the micellar pseudophase, kM', as ethanol content increases: a significant variation of micellar ionization degree could account for this kinetic effect.     

The crystal and molecular structure of the tetraethylammonium salt of tetrahydridopentadecacarbonyltetrarhenate(2−) in two crystallographic forms

The structure of the title compound, (NEt₄)₂[H₄Re₄(CO)₁₅], is reported in two crystallographic modifications, I and II. Both forms axe monoclinic and the cell constants are as follows: I, a 11.355(2), b 21.204(4), c 17.416(3) Å, β 94.15(2)°, space group P2₁/c; II, a 21.831(4), b 17.584(3), c 11.446(2) Å, β 96.02(2)°, space group P2₁,/n. Two sets of 3042 (I) and 2870 (II) independent diffraction intensities, collected by counter methods, were used for the solution and refinement of the two structures. The final conventional R factors have values 5.5% (I) and 6.3% (II), respectively. The crystal packings are compared, showing different conformations of the (NEt₄)⁺ cations. The anions contain a tetrametal cluster formed by an isosceles triangle plus an apically bound metal atom; the carbonyl groups are all terminally bonded to the rhenium atoms. Some differences, present both in the metal atom clusters and in the carbonyl dispositions, are discussed and compared with a third, previously reported, crystallographic modification of the same compound.     

Nucleation of Pd dimers at defect sites of the MgO(100) surface

Point defects on oxide surfaces are presumed to be preferential nucleation sites for supported metal clusters. Under typical growth conditions, dimers constitute the first step in island nucleation. First-principles calculations on the formation of Pd dimers on regular and defect sites of the MgO(100) surface show that nucleation occurs with large dimer binding energies at divacancies and charged oxygen vacancies (F+ centers), while it is less favorable on steps and neutral F centers. The extensive database of defect trapping/attachment properties gives a firm basis to rationalize recent atomic-force microscopy findings and provides guidelines valid, in general, for ionic substrates.