Application of a fractional factorial design for the determination of cadmium by ETA-AAS in different atomization systems

A multivariate study was applied to the investigation of the variables affecting the cadmium sensitivity in a graphite furnace, with and without platform atomization or matrix modifier. The results indicated that, depending on the atomization system used, the factors studied (drying, ashing, atomization, calibration curve) exert an influence on the analysis. The interactions between the factors were also analyzed.     

Coumarin as dipolarophile towards 3,5-dichloro-2,4,6-trimethylbenzonitrile oxide

The reaction of coumarin with the title nitrile oxide gives a single regioisomer in high yield. This result is compared with the dipolarophilic behavior of cinnamic acid esters.     

Instrumental neutron activation analysis of peloids from main Cuban spas

Journal of Radioanalytical and Nuclear Chemistry - Peloids from some Cuban spas (San Diego, Elguea, Santa Lucía, Cajío and Colony) have been studied using Instrumental Neutron Activation...     

Restricted rotation in unbridged sandwich complexes: rotational behavior of closo-[Co(eta 5-NC4H4)(C2B9H11)] derivatives

Rotation about the centroid/metal/centroid axis in ferrocene is facile; the activation energy is 1-5 kcal mol(-1). The structurally similar sandwich complexes derived from closo-[3-Co(eta5-NC4H4)-1,2-C2B9H11] (1) have a different rotational habit. In 1, the cis rotamer in which the pyrrolyl nitrogen atom bisects the carboranyl cluster atoms is 3.5 kcal mol(-1) more stable in energy than the rotamer that is second lowest in energy. This cis rotamer is wide, spanning 216 degrees , and may be split into three rotamers of almost equal energy by substituting the N and the carboranyl carbon atoms adequately. To support this statement, closo-[3-Co(eta5-NC4H4)-1,2-(CH3)2-1,2-C2B9H9] (2), closo-[3-Co(eta5-NC4H4)-1,2-(mu-CH2)3-1,2-C2B9H9] 3, 2-->BF3, and 3-->BF3 have been prepared. Two rotamers are found at low temperature for 2-->BF(3) and 3-->BF3. Compounds 2, 3, and 1-->BF3 behave similarly to 1. Rotational energy barriers and the relative populations of the different energy states are calculated from 1H DNMR spectroscopy (DNMR, dynamic NMR). These results agree with those of semiempirical calculations. Without exception, the cis rotamer is energetically the more stable. The fixed conformation of 1 assists in elucidating the rotational preferences of the [3,3'-Co(1,2-C2B9H11)2]- ion in the absence of steric hindrance; the [3,3'-Co(1,2-C2B9H11)2]- ion is commonly accepted to present a cisoid orientation. Complex 1 is electronically similar to the [3,3'-Co(1,2-C2B9H11)2]- ion. Both have heteroatoms in the pi ligands, and they have the same electronegativity difference between the constituent atoms. This leads to a view of the [NC4H4]- as [7,8-C2B9H11]2- ion, with no steric implications. Therefore the [3,3'-Co(1,2-C2B9H11)2]- ion should be considered to have a cisoid structure, and the different rotamers observed to be the result of steric factors and of the interaction of the counterion with either B-H groups and/or ancillary ligands. The rotamer adopted is the one with the atoms holding the negative charges furthest apart.     

Self-assembly of mercaptane-metallacarborane complexes by an unconventional cooperative effect: a C-H...S-H...H-B hydrogen/dihydrogen bond interaction

The existence of a dihydrogen bond (S-H...H-B) and its combination with a C-H...S hydrogen bond in an unusual cooperative effect are demonstrated from a combination of experimental and theoretical methods. This cooperative effect seems to be responsible for self-assembly of mercaptane-metallacarborane complexes such as closo-[3-Ru(eta6-C6H6)-8-HS-1,2-C2B9H10] (1) and closo-[3-Co(eta5-C5H5)-8-HS-1,2-C2B9H10] (3), which present identical supramolecular two-dimensional polymeric networks. The findings, besides documenting structurally the first S-H...(H-B)2 dihydrogen bond and the unconventional cooperative ability of a boron-attached SH group, prove that substituted carboranes have the potential to serve as building blocks for assembling complex structures.     

Fast high-throughput method for the determination of acidity constants by capillary electrophoresis. II. Acidic internal standards

A fast method for the determination of acidity constants by CZE has been recently developed. This method is based on the use of an internal standard of pK(a) similar to that of the analyte. In this paper we establish the reference pK(a) values of a set of 24 monoprotic neutral acids of varied structure that we propose as internal standards. These compounds cover the most usual working pH range in CZE and facilitate the selection of adequate internal standards for a given determination. The reference pK(a) values of the acids have been established by the own internal standard method, i.e. from the mobility differences between different acids of similar pK(a) in the same pH buffers. The determined pK(a) values have been contrasted to the literature pK(a) values and confirmed by determination of the pK(a) values of some acids of the set by the classical CE method. Some systematic deviations of mobilities have been observed in NaOH buffer in reference to the other used buffers, overcoming the use of NaOH in the classical CE method. However, the deviations affect in a similar degree to the test compounds and internal standards allowing thus, the use of NaOH buffer in the internal standard method. This fact demonstrates the better performance of the internal standard method over the classical method to correct mobility deviations, which together with its fastness makes it an interesting method for the routine determination of accurate pK(a) values of new pharmaceutical drugs and drug precursors.     

2‐Methyl‐1‐phenylsulfanyl‐1,2‐dicarba‐closo‐dodecaborane(12)

In the title o‐carborane derivative, C₉H₁₈B₁₀S, the methyl and phenyl­sulfanyl groups are connected to the C atoms of the carborane cage. The C_cage—C_cage distance is 1.708 (4) Å.     

Supercritical fluid extraction of the volatile oil from Santolina chamaecyparissus

Supercritical fluid extraction (SFE) of the volatile oil from Santolina chamaecyparissus L. flower heads was performed under different conditions of pressure, temperature, mean particle size and CO₂ flow rate. This oil was compared with the essential oil isolated by hydrodistillation (HD). The SFE volatile and essential oils were analysed by GC and GC‐MS. The range of the main volatile components obtained with HD and SFE were, respectively: 1,8‐cineole (25–30% and 7–48%), camphor (7–9% and 8–14%), borneol (7–8% and 2–11%), terpinen‐4‐ol (6–7% and 1–4%), terpinolene (1–4% and 1–7%) and isobornyl acetate (1–2% and 1–11%). The chemical composition of the extracts was greatly influenced by the conditions of pressure and temperature used. In fact, it was possible to enrich the sesquiterpene fraction by increasing the pressure from 8 to 9 MPa, while changing the temperature from 40 to 50°C at 90 bar enriched of the volatiles in n‐alkanes.     

Enrichment of the thymoquinone content in volatile oil from Satureja montana using supercritical fluid extraction

Supercritical fluid extraction (SFE) of the volatile oil from Satureja montana L. was performed under different conditions of pressure (90 and 100 bar), temperature (40 and 50°C), mean particle sizes (0.4, 0.6 and 0.8 mm) and CO₂ flow rate (0.8, 1.1 and 1.3 kg/h) to understand the influence of these parameters on the composition and yield of this oil. The results were compared with those obtained for the essential oil isolated by hydrodistillation (HD). The volatile and the essential oil were analysed by GC and GC‐MS. The main compounds are carvacrol (52.2–62.0% for HD vs. 41.7–64.5% for SFE), thymol (8.6–11.0% for HD vs. 6.0–11.3% for SFE), p‐cymene (6.9–12.8% for HD vs. 6.0–17.8% for SFE), γ‐terpinene (6.4–9.4% for HD vs. 2.3–6.0% for SFE) and β‐bisabolene (2.0–2.7% for HD vs. 2.2–3.5% for SFE). The major difference between SFE and HD was the relative amount of thymoquinone, an oxygenated monoterpene with important biological activities, which can be ten‐fold higher in volatile oil (1.6–3.0 for SFE vs. 0.2% for HD). The morphology of the glandular trichomes of S. montana and the effect of the grinding process on them was also evaluated by SEM.