Femtosecond Terahertz Pulse Propagation Measurements and Simulations of Dewetting Kinetics in Real Time.

We report a terahertz time-domain study of dewetting kinetics on two time scales: femtoseconds and in real time (on the order of minutes). We recorded full electric field terahertz time domain signals with femtosecond time resolution during dewetting of water in cellulose. The femtosecond time-domain signals were analyzed with respect to the amplitude and signal emission times and how these two quantities changed over the course of dewetting kinetics.

A compact Fourier-transform near-infrared spectrophotometer and chemometrics for characterizing a comprehensive set of seized ecstasy samples.

A comprehensive data set of ecstasy samples containing MDMA (N-methyl-3,4-methylenedioxyamphetamine) and MDA (3,4-methylenedioxyamphetamine) seized by the Brazilian Federal Police was characterized using spectral data obtained by a compact, low-cost, near-infrared Fourier-transform based spectrophotometer. Qualitative and quantitative characterization was accomplished using soft independent modeling of class analogy (SIMCA), linear discriminant analysis (LDA) classification, discriminating partial least square (PLS-DA), and regression models based on partial least square (PLS). By applying chemometric analysis, a protocol can be proposed for the in-field screening of seized ecstasy samples.

Near-infrared spectra of liquid and gas samples by diffuse reflectance employing benchtop and handheld spectrophotometers.

This paper describes a new method to obtain NIR spectra of liquid and gas samples by diffuse reflectance, which is especially suitable for handheld spectrophotometers, since most of these instruments are designed to acquire spectrum using this geometry. The core of the method is a diffuse reflectance cell, which consists of a vial containing a mixture of the liquid or gas sample (rare medium) and a powder (dense medium). Using this strategy, no adaptation is required to measure spectra with most portable NIR spectrometers.

Understanding the Metastability of Theophylline FIII by Means of Low-Frequency Vibrational Spectroscopy.

While theophylline has been extensively studied with multiple polymorphs discovered, there is still currently no conclusive structure for the metastable theophylline form III. In this present work, by combining more widely used techniques such as X-ray diffraction and thermogravimetric analysis with more emerging techniques like low-frequency Raman and terahertz time-domain spectroscopy, to analyze the structure and dynamics of a crystalline system, it was possible to provide further evidence that the form III structure has a theophylline monohydrate structure with the water molecules removed. Solid-state density functional theory simulations were paramount in proving that this proposed structure is correct and explain how vibrational modes within the crystal structures feature and govern polymorphic transitions and the metastable form III.

Low-frequency Raman spectrophotometer with wide laser illumination on the sample: A tool for pharmaceutical analytical analysis.

This work describes an optical configuration for a Raman spectrophotometer, which permits variation of the laser spot size from 3 to 3000 μm, maintaining a high Raman photons throughput and allowing acquisitions with a short integration time. In addition, the instrument can acquire spectra from the low to middle frequency vibrational range (10 to 2000 cm), on the Stokes and anti-Stokes sides. One of the features of this new optical configuration is the non-use of beam splitters to redirect the scattered light to the detector, which would sacrifice the laser power.

Comparison of macro and micro Raman measurement for reliable quantitative analysis of pharmaceutical polymorphs.

This work reports on the use of micro- and macro-Raman measurements for quantification of mebendazole (MBZ) polymorphs A, B, and C in mixtures. Three Raman spectrophotometers were studied with a laser spot size of 3, 80 and 100 μm and spectral resolutions of 3.9, 9 and 4 cm, respectively.

Near infrared emission spectroscopy for rapid compositional analysis of Portland cements.

Near infrared emission spectroscopy (NIRES) has been investigated to yield a new analytical method for determination of CaO, SiO, AlO, FeO, MgO, and SO in Portland cement samples. The analyses were accomplished by correlation of the second derivative NIRES spectra with reference elemental analyses made by X-ray Fluorescence (XRF), using Partial Least Square (PLS) regression models. Four different types of cements (type II, III, IV and V) were included in the models.

Multivariate quantification of mebendazole polymorphs by terahertz time domain spectroscopy (THZ-TDS).

This work presents an analytical method based on terahertz-time domain spectroscopy (THz-TDS) and partial least squares (PLS) regression models to quantify mebendazole (MBZ) polymorphs (forms A, B and C) in pharmaceutical raw material. Mebendazole polymorphs A, B and C were quantified with RMSEP values of 1.5% w/w, 1.

iHEART: a miniaturized near-infrared in-line gas sensor using heart-shaped substrate-integrated hollow waveguides.

A novel heart-shaped substrate-integrated hollow waveguide (hiHWG) was integrated with a near-infrared micro-spectrometer (μNIR) for sensing natural gases, resulting in an ultra-compact near-infrared gas sensing system - iHEART. The iHEART system was evaluated using two different μNIR spectrometers, and the performance was compared with a laboratory NIR spectrometer for gas analysis based on an acousto-optic tunable filter (AOTF). The spectral data were pre-processed using the 1(st) derivative Savitzky-Golay algorithm, and then used for establishing multivariate regression models based on partial least squares (PLS).

Electric field-assisted solid phase extraction and cleanup of ionic compounds in complex food matrices: Fluoroquinolones in eggs.

The use of electric fields as additional driving forces in sample preparation techniques is an innovative approach that is environmentally friendly, straightforward, and able to overcome several limitations of conventional sample preparation procedures. In this work, the advantages of electric field-assisted solid phase extraction (E-SPE) using syringe-type cartridges were demonstrated for the extraction of four fluoroquinolones (FQs) in their anionic forms. The FQs were extracted from eggs and subsequently determined by UHPLC-MS/MS.

Determination of detergent and dispensant additives in gasoline by ring-oven and near infrared hypespectral imaging.

A method using the ring-oven technique for pre-concentration in filter paper discs and near infrared hyperspectral imaging is proposed to identify four detergent and dispersant additives, and to determine their concentration in gasoline. Different approaches were used to select the best image data processing in order to gather the relevant spectral information. This was attained by selecting the pixels of the region of interest (ROI), using a pre-calculated threshold value of the PCA scores arranged as histograms, to select the spectra set; summing up the selected spectra to achieve representativeness; and compensating for the superimposed filter paper spectral information, also supported by scores histograms for each individual sample.

A new approach to polarimetric measurements based on birefringent crystals and diode lasers.

A new polarimetric instrument and measurement method is described based on the use of diode lasers as radiation source (532, 650 and 1064nm) and birefringent prisms, such as Glan-Laser and Wollaston, as analyzers. The laser radiation is passed through a dichroic polarizer film for further orientation of its polarization plane at 45° in relation to the polarization plane of the analyzer. The polarized beam, oriented in that way, passes the sample cell, impinges the prism surface, and the intensities of the two emerged beams are detected by two twin silicon detectors.

A microfluidic device with integrated fluorimetric detection for flow injection analysis.

This work describes the development of flow analysis microsystems with integrated fluorimetric detection cells. Channels (width of 300-540 microm and depth of 200-590 microm) were manufactured by deep-UV lithography in urethane-acrylate (UA) resin. Plastic optical fibers (diameter of 250 microm) were coupled to a 2.

Assessment of infrared spectroscopy and multivariate techniques for monitoring the service condition of diesel-engine lubricating oils.

This paper presents two methodologies for monitoring the service condition of diesel-engine lubricating oils on the basis of infrared spectra. In the first approach, oils samples are discriminated into three groups, each one associated to a given wear stage. An algorithm is proposed to select spectral variables with good discriminant power and small collinearity for the purpose of discriminant analysis classification.

Determination of pentavalent antimony in antileishmaniotic drugs using an automated system for liquid-liquid extraction with on-line detection.

An automated system for liquid-liquid extraction flow analysis (LLE-FA) for the determination of Sb(V) in antileishmanial drugs is presented. The method is based on extraction in a 5mL glass extraction chamber of an ion pair formed between hexachloroantimoniate anion and rhodamine B cation into toluene. The detection system consists of a green light emitting diode (LED) and a photodiode.

Determination of phosphate in natural water employing a monosegmented flow system with simultaneous multiple injection.

A monosegmented flow system was employed for the determination of low contents of phosphate in natural water. In this approach, sample and reagents are simultaneously injected to a PTFE reaction coil where the homogenization of the mixture occurs while the monosegment is pumped forwards the photometric detector. The proposed system was evaluated by determining phosphate ion, based on the reaction of association between molybdophosphate and malachite green.

Application of amperometric sol-gel biosensor to flow injection determination of glucose.

A glucose biosensor with enzyme immobilised by sol-gel technology was constructed and evaluated. The glucose biosensor reported is based on encapsulated GOX within a sol-gel glass, prepared with 3-aminopropyltriethoxy silane, 2-(3,4-epoxycyclohexyl)-ethyltrimetoxy silane and HCl. A flow system incorporating the amperometric biosensor constructed was developed for the determination of glucose in the 1x10(-4)-5x10(-3) moll(-1) range with a precision of 1.

Effect of ethanol in the organic phase on liquid-liquid extraction in monosegmented flow analysis. Determination of zinc in drugs.

In liquid-liquid extraction performed by monosegmented flow analysis (MSFA), the aqueous sample is introduced between two air bubbles and flows, under restricted dispersion, through a glass extraction tube where the analyte is retained, usually at pH higher than 8. The retained analyte is removed to a small volume of an organic phase containing a ligand which is introduced after the second air bubble. In this work, the effect of the organic phase composition on the extraction of Cu(II), Zn(II) and Cd(II) in MSFA systems was investigated by changing the ethanol content (0.

Design and development of a multichannel potentiometer for monitoring an electrode array and its application in flow analysis.

A versatile potentiometer that works with electrode arrays in flow injection and/or monosegmented flow systems is described. The potentiometer is controlled by a microcomputer that allows individual, sequential multiplexed or random accesses to eight electrodes while employing only one reference electrode. The instrument was demonstrated by monitoring an array of seven flow-through ion-selective electrodes for Ag+ and for three electrodes for Cl(-), Ca2+ and K+.

Simultaneous determination of methanol and ethanol in gasoline using NIR spectroscopy: effect of gasoline composition.

Near infrared (NIR) spectroscopy was employed for simultaneous determination of methanol and ethanol contents in gasoline. Spectra were collected in the range from 714 to 2500 nm and were used to construct quantitative models based on partial least squares (PLS) regression. Samples were prepared in the laboratory and the PLS regression models were developed using the spectral range from 1105 to 1682 nm, showing a root mean square error of prediction (RMSEP) of 0.

Construction and evaluation of a flow injection micro-analyser based on urethane-acrylate resin.

A flow injection micro-analyser with an integrated injection device and photometric detection is described. Channels measuring 205-295 microm depth by 265-290 microm maximum width were manufactured by deep UV lithography on two layers of urethane-acrylate oligomers-based photoresist. Hypodermic syringe needles (450 microm diameter) were connected to the channels for introduction of solutions into the system.

A monosegmented-flow Karl Fischer titrator.

A monosegmented volumetric Karl Fischer titrator is described to mechanize the determination of water content in organic solvents. The system is based on the flow-batch characteristics of the monosegmented analysis concept and employs biamperometry to monitor the progress of the titration. The system shows accuracy and precision that are highly independent of the flow rate, does not require calibration, and is carried out in a closed system capable of minimizing contact of the sample and reagents with ambient moisture.

A new approach to flow-batch titration. A monosegmented flow titrator with coulometric reagent generation and potentiometric or biamperometric detection.

Monosegmented flow analysis (MSFA) has been used as a flow-batch system to produce a simple, robust, and mechanized titrator that enables true titrations to be performed without the use of standards. This paper also introduces the use of coulometry with monosegmented titration by proposing a versatile flow cell. Coulometric generation of the titrand is attractive for titrations performed in monosegmented systems, because the reagent can be added without increasing the volume of sample injected.

Silicone sensing phase for detection of aromatic hydrocarbons in water employing near-infrared spectroscopy.

The use of silicone for detection of aromatic hydrocarbons in water using near-infrared spectroscopy is proposed. A sensing phase of poly(dimethylsiloxane) (PDMS) was prepared, and a rod of this material was adapted to a transflectance probe for measurements from 850 to 1800 nm. Deionized water samples contaminated separately with known amounts of benzene, toluene, ethylbenzene, and m-xylene were used for evaluation of the PDMS sensing phase, and measurements were made in a closed reactor with constant stirring.

Chloride-selective membrane electrodes and optodes based on an indium(III) porphyrin for the determination of chloride in a sequential injection analysis system.

Two quasi-independent methods for potentiometric and optical determination of chloride were simultaneously implemented in a flow system, providing real-time assessment of the quality of results. A potentiometric and an optical polymeric membrane doped with the same indium(III) octaethyl-porphyrin were used as sensor ionophore. The working mechanism and the analytical characteristics of these porphyrin-based sensors with respect to dynamic range, selectivity, repeatability and lifetime are discussed.