Utilizing relativistic effective core potentials for accurate calculations of molecular polarizabilities on transition metal compounds

The requirements necessary to extend an ECP basis set for the calculation of electric and linear optical properties to the transition metals are studied. Previously an augmentation of the SBK basis set for 39 elements with s and p electron only valences (H-Rn, excluding Ga, In, and Tl) [J. Comput. Chem., 2005, 26, 1464-1471] was presented. In this work, electric dipole moments, polarizabilities, and anisotropies of selected metal hydrides, sulfides, and bromides, cisplatin, and the Fe, Ru, and Os metallocene derivatives along with many other systems are calculated and discussed. ECP calculations of molecules containing 3d and 4d metal centers among main group atoms have good agreement, often within 1-2% of the all-electron result at the time-dependent Hartree-Fock (TDHF)/Sadlej level of theory. Molecules with a 5d metal center have a large difference from and are more accurate than the all-electron results due to the inclusion of relativistic effects in the ECPs. The polarizability as calculated with and without ECPs of metallic clusters and surfaces is increasingly different as atomic number increases, again due to a lack of relativistic effects in the all-electron calculations. The augmented ECP calculations are consistent with relativistic all-electron results, while the Sadlej calculations are consistent with other nonrelativistic results. Both relativistic and basis set effects are less noticeable when the metal is in a formally positive state.     

Application of high-performance liquid chromatography-nuclear magnetic resonance coupling to the identification of limonoids from mahogany tree (Switenia macrophylla, Meliaceae) by stopped-flow 1D and 2D NMR spectroscopy

Separation and characterization of limonoids from Switenia macrophylla (Meliaceae) by HPLC-NMR technique has been described. Analyses were carried out using reversed-phase gradient HPLC elution coupled to NMR (600 MHz) spectrometer in stopped-flow mode. Separated peaks were collected into an interface unit prior to NMR measurements, which were performed with suppression of solvent signals by shaped pulses sequences. Structure elucidation of the limonoids was attained by data obtained from 1H NMR, TOCSY, gHSQC and gHMBC spectra without conventional isolation that is usually applied in natural products studies.     

Automated analysis of 2-methyl-3-furanthiol and 3-mercaptohexyl acetate at ng L(-1) level by headspace solid-phase microextracion with on-fibre derivatisation and gas chromatography-negative chemical ionization mass spectrometric determination

A new method was used for the extraction of organophosphorus pesticides (OPPs) from water samples: dispersive liquid-liquid microextraction (DLLME) coupled with gas chromatography-flame photometric detection (GC-FPD). In this extraction method, a mixture of 12.0 microL chlorobenzene (extraction solvent) and 1.00 mL acetone (disperser solvent) is rapidly injected into the 5.00 mL water sample by syringe. Thereby, a cloudy solution is formed. In fact, the cloudy state is because of the formation of fine droplets of chlorobenzene, which has been dispersed among the sample solution. In this step, the OPPs in water sample are extracted into the fine droplets of chlorobenzene. After centrifuging (2 min at 5000 rpm), the fine droplets of chlorobenzene are sedimented in the bottom of the conical test tube (5.0+/-0.3 microL). Sedimented phase (0.50 microl) is injected into the GC for separation and determination of OPPs. Some important parameters, such as kind of extraction and disperser solvent and volume of them, extraction time, temperature and salt effect were investigated. Under the optimum conditions, the enrichment factors and extraction recoveries were high and ranged between 789-1070 and 78.9-107%, respectively. The linear range was wide (10-100,000 pg/mL, four orders of magnitude) and limit of detections were very low and were between 3 to 20 pg/mL for most of the analytes. The relative standard deviations (RSDs) for 2.00 microg/L of OPPs in water with internal standard were in the range of 1.2-5.6% (n=5) and without internal standard were in the range of 4.6-6.5%. The relative recoveries of OPPs from river, well and farm water at spiking levels of 50, 500 and 5000 pg/mL were 84-125, 88-123 and 93-118%, respectively. The performance of proposed method was compared with solid-phase microextraction (SPME) and single drop microextraction. DLLME is a very simple and rapid (less than 3 min) method, which requires low volume of sample (5 mL). It also has high enrichment factor and recoveries for extraction of OPPs from water.     

Method optimization by solid-phase microextraction in combination with gas chromatography with mass spectrometry for analysis of beer volatile fraction

A simple and sensitive method for the analysis of beer volatile compounds was optimised using headspace solid-phase microextraction (SPME) and gas chromatography with mass detection. Headspace SPME using a 75 microm Carboxen-polydimethylsiloxane (CAR-PDMS) fiber provided effective sample enrichment and enabled extraction of a wide variety of compounds. The reproducibility depended on the compounds, with a mean value of 1.4% for alcohols, 3.3% for ethers, 6.7% for aldehydes, 3.4% for acids, 1.7% for aromatic compounds, 2.4% for esters, 7.4% for hydrocarbons, 1.8% for alicyclic compounds, and 3.4% for heterocyclic compounds. The optimised methodology can be used to compare volatile profile from different types of beers and eventually to study the evolution of a particular beer during aging.     

Lead post-mortem intake in human bones of ancient populations by (109)Cd-based X-ray fluorescence and EDXRF

In this work we measured the lead concentration in human bones of Middle Age by means of a portable X-ray fluorescence system based on ¹⁰⁹Cd radioactive source. The detection system consists on a Ge hyperpure detector. This system, conceived for in vivo Pb analysis in bone, is portable, non-destructive and is based on lead K lines detection.

The analysed bones are part of two collections of bones both from the end of Middle Age and submitted for some years to a lead polluted burial environment. The bones of one collection were buried initially on the soil in a convent, in Lisbon (Portugal) and further on, kept in a lead coffin for around 100 years. The second collection contains bones buried permanently on the soil around an old church on the south of Portugal. This place became a parking car for around 20 years.

In this work we studied the distribution of Pb in cortical bone, and trabecular regions from the outside surface to the inner part of the bone and the results are compared with the obtained ones by energy dispersive X-ray fluorescence (EDXRF).

The obtained values present a strong contamination of Pb in spongy bones kept in the lead coffin with concentrations ranging from 250 to 350 μg Pb/g bone mineral, and 4 to 7 μg Pb/g bone mineral for bones buried in the soil. Good agreement was observed between the results obtained by the two techniques.     

Interpretation of non-Nernstian slopes in graphic analysis of data collected in pH range close to deprotonation of a ligand Part I. A glass electrode potentiometric and polarographic study of Cd-(TAPSO)x-(OH)y and Zn-(TAPSO)x-(OH)y systems

In this work, the complexation of cadmium and zinc ions by 3-[N-tris(hydroxymethyl)methylamine]-2-hydroxypropanesulfonic acid (TAPSO), a commercial biological buffer, was evaluated using three electrochemical techniques, at fixed total-ligand and total-metal concentration ratio and varied pH, at 25.0+/-0.1 degrees C and ionic strength set to 0.1M KNO(3). For both metal-ligand systems, complexation was evidenced in the pH range close to deprotonation of the ligand and the final models were optimised after a meticulous graphical analysis. For Cd-(TAPSO)(x)-(OH)(y) system, two complexes, CdL and CdL(2), were identified in the buffering region of the ligand. The proposed final model for this system is: CdL, CdL(2) and CdL(2)(OH) with stability constants, as logbeta, of 2.2, 4.2 and 8.6, respectively. For Zn-(TAPSO)(x)-(OH)(y) system, the complex ZnL is the main species formed in the buffering pH range. The proposed final model is ZnL, ZnL(OH) and ZnL(OH)(2) with overall refined stability constants (as logbeta) to be: 2.5, 7.2 and 13.2, respectively.     

Experimental and theoretical elastic cross sections for electron collisions with the C3H6 isomers

In the present work we report cross sections for electron collisions with the isomers propene (C3H6) and cyclopropane (c-C3H6). Electron-scattering differential cross sections (DCS) are reported for measurements carried out for energies 1.5-100 eV and the angular range of 20 degrees-120 degrees. Elastic integral cross sections (ECS), DCS, and momentum-transfer cross sections (MTCS) are reported for calculations carried out using the Schwinger multichannel method with pseudopotentials for the energy range of 2.0-40 eV and angular range of 0 degrees-180 degrees. The resemblance of the pi* shape resonance in the cross sections, observed at 1.5-2.0 eV for propene, to those in C2H4 and C2F4 clearly points to the effect of the double bond in the molecular structures for these molecules. Below 60 eV, we observed clear differences in peak positions and magnitudes between the DCS, ECS, and MTCS for C3H6 and c-C3H6, which we view as the isomer effect.     

Separation and preconcentration procedures for the determination of lead using spectrometric techniques: a review

Lead is recognized worldwide as a poisonous metal. Thus, the determination of this element is often required in environmental, biological, food and geological samples. However, these analyses are difficult because such samples contain relatively low concentrations of lead, which fall below the detection limit of conventional analytical techniques such as flame atomic absorption spectrometry and inductively coupled plasma optical emission spectrometry. Several preconcentration procedures to determine lead have therefore been devised, involving separation techniques such as liquid-liquid extraction, solid phase extraction, coprecipitation and cloud point extraction. Citing 160 references, this paper offers a critical review of preconcentration procedures for determining lead using spectroanalytical techniques.     

Multivariate technique for optimization of digestion procedure by focussed microwave system for determination of Mn, Zn and Fe in food samples using FAAS

This article describes the development by response surface methodology (RSM) of a procedure for iron, zinc and manganese determination by flame atomic absorption spectrometry (FAAS) in food samples after digestion employing a focussed microwave system. A Doehlert matrix was used to find optimal conditions for the procedure through response surface study. Three variables (irradiation power and time and composition of oxidant solution—HNO₃ + H₂O₂) were regarded as factors in the optimization study. The working conditions were established as a compromise between optimum values found for each analyte taking into consideration the robustness of the procedure. These values were 12 min, 260 W and 42% (v/v) for irradiation time, irradiation power and percent of H₂O₂ in solution, respectively. The accuracy of the optimized procedure was evaluated by analysis of certified reference materials and by comparison with a well-established closed vessel microwave dissolution methodology.     

2-Diazoacetoacetic acid, an efficient and convenient reagent for the synthesis of alpha-diazo-beta-ketoesters

The formation of various alpha-diazo acetoacetic esters can be obtained in a single transformation with good to excellent yields using readily available 2-diazoacetoacetic acid.