Investigation of Sulfonium-Iodide-Based Ionic Liquids to Inhibit Corrosion of API 5L X52 Steel in Different Flow Regimes in Acid Medium.

The present work deals with the corrosion inhibition mechanism of API 5L X52 steel in 1 M H2SO4 employing the ionic liquid (IL) decyl(dimethyl)sulfonium iodide [DDMS+I-]. Such a mechanism was elicited by the polarization resistance (R p), potentiodynamic polarization (PDP), and electrochemical impedance spectroscopy (EIS) techniques, both in stationary and dynamic states. The electrochemical results indicated that the corrosion inhibition was controlled by a charge transfer process and that the IL behaved as a mixed-type corrosion inhibitor (CI) with anodic preference. The experimental results revealed maximal inhibition efficiency (IE) rates up to 93% at 150 ppm in the stationary state, whereas in turbulent flow, the IE fell to 65% due to the formation of microvortexes that promoted higher desorption of IL molecules from the surface. The Gibbs free energy of adsorption (ΔG°ads) value of -34.89 kJ mol-1, obtained through the Langmuir isotherm, indicated the formation of an IL monolayer on the metal surface by combining physisorption and chemisorption. The surface analysis techniques confirmed the presence of Fe x O y , FeOOH, and IL on the surface and showed that corrosion damage diminished in the presence of IL. Furthermore, the quantum chemistry calculations (DFT) indicated that the iodide anion hosted most of the highest occupied molecular orbital (HOMO), which eased its adsorption on the anodic sites, preventing the deposition of sulfate ions on the electrode surface.

Application of an emulsified polycolloid substrate biobarrier to remediate petroleum-hydrocarbon contaminated groundwater.

Emulsified polycolloid substrate (EPS) was developed and applied in situ to form a biobarrier for the containment and enhanced bioremediation of a petroleum-hydrocarbon plume. EPS had a negative zeta potential (-35.7 mv), which promoted its even distribution after injection. Batch and column experiments were performed to evaluate the effectiveness of EPS on toluene containment and biodegradation. The EPS-to-water partition coefficient for toluene (target compound) was 943. Thus, toluene had a significant sorption affinity to EPS, which caused reduced toluene concentration in water phase in the EPS/water system. Groundwater containing toluene (18 mg/L) was pumped into the three-column system at a flow rate of 0.28 mL/min, while EPS was injected into the second column to form a biobarrier. A significant reduction of toluene concentration to 0.1 mg/L was observed immediately after EPS injection. This indicates that EPS could effectively contain toluene plume and prevent its further migration to farther downgradient zone. Approximately 99% of toluene was removed after 296 PVs of operation via sorption, natural attenuation, and EPS-enhanced biodegradation. Increase in total organic carbon and bacteria were also observed after EPS supplement. Supplement of EPS resulted in a growth of petroleum-hydrocarbon degrading bacteria, which enhanced the toluene biodegradation.

Assignment and conformational investigation of asymmetric phenylindenylidene ruthenium complexes bearing N,O-bidentate ligands.

The NMR conformational study of three asymmetric phenylindenylidene ruthenium complexes 4.1-4.3, is presented. Complete (1)H and (13)C assignments could be obtained for 4.1-4.3 in benzene solution from multiple 2D homonuclear and heteronuclear NMR techniques. Our NMR analysis shows that each complex exists as a 55:45 mixture of two rotational isomers in slow exchange on the NMR chemical shift timescale. They are shown to be related by a 180 degrees flip of the indenylidene ligand along the Ru=CR bond. Both rotational isomers can be discriminated by means of NOEs contacts between the various ligands coordinating to the Ru. By matching these stereospecific assignments to the chemical shift, a chemical shift based fingerprint of the isomers that may allow straightforward assignment of future asymmetric phenylindenylidene ruthenium complexes is proposed.

Implementation of a process analytical technology system in a freeze-drying process using Raman spectroscopy for in-line process monitoring.

The aim of the present study was to propose a strategy for the implementation of a Process Analytical Technology system in freeze-drying processes. Mannitol solutions, some of them supplied with NaCl, were used as models to freeze-dry. Noninvasive and in-line Raman measurements were continuously performed during lyophilization of the solutions to monitor real time the mannitol solid state, the end points of the different process steps (freezing, primary drying, secondary drying), and physical phenomena occurring during the process. At-line near-infrared (NIR) and X-ray powder diffractometry (XRPD) measurements were done to confirm the Raman conclusions and to find out additional information. The collected spectra during the processes were analyzed using principal component analysis and multivariate curve resolution. A two-level full factorial design was used to study the significant influence of process (freezing rate) and formulation variables (concentration of mannitol, concentration of NaCl, volume of freeze-dried sample) upon freeze-drying. Raman spectroscopy was able to monitor (i) the mannitol solid state (amorphous, alpha, beta, delta, and hemihydrate), (ii) several process step end points (end of mannitol crystallization during freezing, primary drying), and (iii) physical phenomena occurring during freeze-drying (onset of ice nucleation, onset of mannitol crystallization during the freezing step, onset of ice sublimation). NIR proved to be a more sensitive tool to monitor sublimation than Raman spectroscopy, while XRPD helped to unravel the mannitol hemihydrate in the samples. The experimental design results showed that several process and formulation variables significantly influence different aspects of lyophilization and that both are interrelated. Raman spectroscopy (in-line) and NIR spectroscopy and XRPD (at-line) not only allowed the real-time monitoring of mannitol freeze-drying processes but also helped (in combination with experimental design) us to understand the process.

Assessment of the solid-state composition of an active salicylanilide compound by FT-Raman spectroscopy.

A biologically active salicylanilide compound currently appears in three known solid-state forms: polymorph I (Pol I), polymorph II (Pol II) and the amorphous form (Amorph). The obtained FT-Raman spectra revealed several regions of interest (ROIs) qualitatively distinguishing the different forms, allowing samples with an unknown polymorphic composition to be quantitatively analysed by FT-Raman spectroscopy. The Markov-transformed peak areas of the Raman-bands in the ROIs from the samples were determined and compared with the transformed peak areas obtained for the reference solid-state forms. A constrainted linear regression model estimated the contribution of each reference to the different samples. The applicability of this approach was demonstrated by analysing commercially available batches.

Influence of particle size on the quantitative determination of salicylic acid in a pharmaceutical ointment using FT-Raman spectroscopy.

A second order polynomial calibration model was developed and statistically validated for the direct and non-destructive quantitative analysis - without sample preparation - of the active pharmaceutical ingredient (API) salicylic acid in a pharmaceutical ointment using FT-Raman spectroscopy. The calibration curve was modeled by plotting the peak intensity of the vector normalized spectral band between 757 and 784cm(-1) against the known salicylic acid concentrations in standards. At this band, no spectral interferences from the ointment vehiculum (white vaseline) are observed. For the validation of the polynomial model, its fit and its predictive properties were evaluated. The validated model was used for the quantification of 25 ointments, compounded by different retail pharmacists. The same standards and samples were used, both for development and validation of a regression model and for quantitative determination by HPLC - with sample preparation - as described for the related substances of salicylic acid in the Ph. Eur. IV. The quantification results obtained by the FT-Raman method corresponded with the HPLC results (p=0.22), provided that the particle size of salicylic acid in the standards is the same as in the analyzed samples. The non-destructive FT-Raman method is a reliable alternative for the destructive HPLC method, as it is faster and does not require sample pre-treatment procedures.

Determination of the relative amounts of three crystal forms of a benzimidazole drug in complex finished formulations by FT-Raman spectroscopy.

A 5% (m/m) premix for animal use was quantitatively characterized for the polymorph composition of its benzimidazole drug substance. Raman spectra of reference samples (pure polymorphs A, B and C in lactose at a concentration of 5%, m/m) were compared with the spectra of benzimidazole samples with a known polymorph composition and with the spectra of uncharacterized premixes. The raw intensities of 78 selected wavenumbers were vector-normalized and application of stepwise linear regression models estimated the relative quantities of the benzimidazole-drug polymorphs A, B and C in the different samples. Modelling results of the samples with known polymorph composition were in compliance with the expected concentrations, validating the proposed methodology. The benzimidazole drug substance in the premixes was predominantly polymorph B. Although statistically not significant, some traces of polymorph A could not be ruled out. Similar analyses were performed to evaluate the solid-state stability of the benzimidazole drug substance in another drug formulation, i.e. a suspension-emulsion. Suspension-emulsions originally determined as containing polymorph B benzimidazole drug substance were stored for 12 months at 25 degrees C/60%RH. FT-Raman spectroscopy revealed that no polymorph transformations occurred during this storage.

Development and validation of a direct, non-destructive quantitative method for medroxyprogesterone acetate in a pharmaceutical suspension using FT-Raman spectroscopy.

A simple linear regression method was developed and statistically validated for the direct and non-destructive quantitative analysis--without sample preparation--of the active pharmaceutical ingredient (API) medroxyprogesterone acetate (MPA) in an aqueous pharmaceutical suspension (150 mg in 1.0 ml) using FT-Raman spectroscopy. The linear regression was modelled by plotting the highest peak intensity of the vector normalized spectral band between 1630 and 1590 cm-1 against different MPA standard suspension concentrations. At this band, no spectral interferences from additives in the suspension are observed. The validated model was used for the quantification of a commercial suspension (150 mg in 1.0 ml) of the commercialized preparations. The same standards and samples were used, respectively, for the development and validation of a simple linear regression model and for the quantitative determination by means of HPLC-with sample preparation-as described for the related substances of MPA in the Ph. Eur. IV. The quantification results obtained by the FT-Raman method corresponded with the claimed label concentration (150.01+/-0.96 mg/ml (n=6)). Applying the HPLC method, however, a systematic error was observed (157.77+/-0.94 mg/ml (n=6)). The direct FT-Raman method hence appears the most reliable for the quantification of the MPA component in suspension, compared to the HPLC method that requires sample preparation. The latter method provides a systematic error because the exact volume or density of a suspension sample is unknown. A precise isolation of fixed volumes from a suspension is rather unfeasible because of the continuous sagging of the suspended particles and their sticking to the used materials in the isolation process.

In-line monitoring of a pharmaceutical blending process using FT-Raman spectroscopy.

FT-Raman spectroscopy (in combination with a fibre optic probe) was evaluated as an in-line tool to monitor a blending process of diltiazem hydrochloride pellets and paraffinic wax beads. The mean square of differences (MSD) between two consecutive spectra was used to identify the time required to obtain a homogeneous mixture. A traditional end-sampling thief probe was used to collect samples, followed by HPLC analysis to verify the Raman data. Large variations were seen in the FT-Raman spectra logged during the initial minutes of the blending process using a binary mixture (ratio: 50/50, w/w) of diltiazem pellets and paraffinic wax beads (particle size: 800-1200 microm). The MSD-profiles showed that a homogeneous mixture was obtained after about 15 min blending. HPLC analysis confirmed these observations. The Raman data showed that the mixing kinetics depended on the particle size of the material and on the mixing speed. The results of this study proved that FT-Raman spectroscopy can be successfully implemented as an in-line monitoring tool for blending processes.