Fourier Transform Infrared Measurements Research Articles

A Bayesian Estimation Model for Transient Engine Exhaust Characterization Using Fourier Transform Infrared Spectroscopy

Comprehensive emissions models extensively use engine exhaust data from vehicle experiments to represent the relationship between fuel composition and pollutants. However, the predicted emissions from these models often neglect the effects of transients and speed-load history. Fourier transform infrared (FTIR) spectroscopy is a high frequency measurement technique capable of comprehensive speciation. However, due to long residence times of exhaust within a FTIR spectrometer gas cell, FTIR measurements are contaminated by the effects of historical emissions, precluding the attainment of time-resolved engine exhaust data. This work presents a Bayesian estimation model for processing FTIR measurements to obtain accurate estimations of instantaneous engine exhaust composition. The Bayesian model utilizes a simple model of the mixing dynamics of the gas cell and measurement noise statistics to estimate the composition of exhaust entering the FTIR gas cell during a measurement period. To validate the estimation...

FTIR Measurement of Cellulose Microfibril Angle in Historic Scots Pine Wood and Its Use to Detect Fungal Decay

ABSTRACTMicrofibril angle (MFA) – the orientation of cellulose fibres in the S2 layer of the secondary cell wall – is a key determinant of the stiffness and strength of timber. The microfibril angle depends on the way in which the timber was grown and its position within the tree. Microfibril angle can be measured by X-ray diffraction and other methods, but the methods in current use are slow or require advanced instrumentation. The aim of this study was to explore the use of polarised Fourier transform infrared (FTIR) microscopy as a relatively fast and inexpensive method for measuring MFA in historic Scots pine (Pinus sylvestris L.). The FTIR measurements were calibrated against X-ray measurements of MFA in modern Scots pine. We observed a wide range in MFA values and a radial pattern of MFA similar to modern Scots pine in undecayed Scots pine heartwood from sixteenth and seventeenth century beams in Scottish secular buildings. The density of the heartwood was also similar to modern plantation-grown Scots pine despite the much slower growth rate recorded in the ring widths of the historic timber. The sapwood, which had been attacked by both insect pests and fungi, showed an erratic reduction in density and a large increase in MFA compared to the modern material. The increased sapwood MFA was attributed to selective destruction of the S2 layer of the wood cell walls by fungal decay. Using MFA measurements in conjunction with density offers the possibility to estimate the mechanical properties of sound historic pine timber, to detect fungal decay more sensitively than by density alone, and to distinguish between pest and fungal attack in a way that relates directly to the remaining mechanical performance of the timber.

Investigation of Reaction Mechanism of NO-C3H6-CO-O2 Reaction over NiFe2O4 Catalyst.

To elucidate the reaction mechanism of NO–C3H6–CO–O2 over NiFe2O4, we investigated the dynamics of the adsorbed and gaseous species during the reaction using operando Fourier transform infrared (FTIR). The NO reduction activity dependent on the C3H6 and CO concentrations suggested that NO is reduced by C3H6 under three-way catalytic conditions. From FTIR measurements and kinetic analysis, it was clarified that the acetate species reacted with NO–O2 to form N2 via NCO, and that the rate-limiting step of NO reduction was the reaction between CH3COO– and NO–O2. The NO reduction mechanism of the three-way catalyst on NiFe2O4 is different to that on platinum-group metal catalysts, on which NO reduction proceeds through N–O cleavage.

Microtiter plate cultivation of oleaginous fungi and monitoring of lipogenesis by high-throughput FTIR spectroscopy

BackgroundOleaginous fungi can accumulate lipids by utilizing a wide range of waste substrates. They are an important source for the industrial production of omega-6 polyunsaturated fatty acids (gamma-linolenic and arachidonic acid) and have been suggested as an alternative route for biodiesel production. Initial research steps for various applications include the screening of fungi in order to find efficient fungal producers with desired fatty acid composition. Traditional cultivation methods (shake flask) and lipid analysis (extraction-gas chromatography) are not applicable for large-scale screening due to their low throughput and time-consuming analysis. Here we present a microcultivation system combined with high-throughput Fourier transform infrared (FTIR) spectroscopy for efficient screening of oleaginous fungi.ResultsThe microcultivation system enables highly reproducible fungal fermentations throughout 12 days of cultivation. Reproducibility was validated by FTIR and HPLC data. Analysis of FTIR spectral ester carbonyl peaks of fungal biomass offered a reliable high-throughput at-line method to monitor lipid accumulation. Partial least square regression between gas chromatography fatty acid data and corresponding FTIR spectral data was used to set up calibration models for the prediction of saturated fatty acids, monounsaturated fatty acids, polyunsaturated fatty acids, unsaturation index, total lipid content and main individual fatty acids. High coefficients of determination (R2 = 0.86–0.96) and satisfactory residual predictive deviation of cross-validation (RPDCV = 2.6–5.1) values demonstrated the goodness of these models.ConclusionsWe have demonstrated in this study, that the presented microcultivation system combined with rapid, high-throughput FTIR spectroscopy is a suitable screening platform for oleaginous fungi. Sample preparation for FTIR measurements can be automated to further increase throughput of the system.

Water-bearing, high-pressure Ca-silicates

Water-bearing minerals provide fundamental knowledge regarding the water budget of the mantle and are geophysically significant through their influence on the rheological and seismic properties of Earth's interior. Here we investigate the CaO–SiO2–H2O system at 17 GPa and 1773 K, corresponding to mantle transition-zone condition, report new high-pressure (HP) water-bearing Ca-silicates and reveal the structural complexity of these phases. We document the HP polymorph of hartrurite (Ca3SiO5), post-hartrurite, which is tetragonal with space group P4/ncc, a=6.820(5), c=10.243(8) Å, V=476.4(8) Å3, and Z=4, and is isostructural with Sr3SiO5. Post-hartrurite occurs in hydrous and anhydrous forms and coexists with larnite (Ca2SiO4), which we find also has a hydrous counterpart. Si is 4-coordinated in both post-hartrurite and larnite. In their hydrous forms, H substitutes for Si (4H for each Si; hydrogrossular substitution). Fourier transform infrared (FTIR) spectroscopy shows broad hydroxyl absorption bands at ∼3550 cm−1 and at 3500–3550 cm−1 for hydrous post-hartrurite and hydrous larnite, respectively. Hydrous post-hartrurite has a defect composition of Ca2.663Si0.826O5H1.370 (5.84 weight % H2O) according to electron-probe microanalysis (EPMA), and the Si deficiency relative to Ca is also observed in the single-crystal data. Hydrous larnite has average composition of Ca1.924Si0.851O4H0.748 (4.06 weight % H2O) according to EPMA, and it is in agreement with the Si occupancy obtained using X-ray data collected on a single crystal. Superlattice reflections occur in electron-diffraction patterns of the hydrous larnite and could indicate crystallographic ordering of the hydroxyl groups and their associated cation defects. Although textural and EPMA-based compositional evidence suggests that hydrous perovskite may occur in high-Ca-containing (or low silica-activity) systems, the FTIR measurement does not show a well-defined hydroxyl absorption band for this phase, implying the water content, at least in the quenched glass, is below the limit of detection (100–1000 ppm). We conclude that at high pressure, as at ambient pressure, some calcium silicates have a high affinity for H2O and high dehydration temperatures. The thermal stability of these hydrous phases suggests that they could exist along a typical mantle geotherm and thus they might be relevant for understanding the mineralogy and water content of Earth's mantle.

Electrochemical Impedance Spectroscopy of Polyvinylalcohol Based Gel Electrolyte

Research on the effect of electrolyte ammonium salt, concentration electrolyte with plasticizer to ionic and electronic conductivity of polymer gel electrolyte has been conducted with the variations of two electrolyte NH 4 Cl-PVA and NH 4 SCN-PVA at a concentration of 10, 30, 40 (wt%). The measurement of using ionic conductivity by using impedance spectroscopy method showed that the highest value was 0.0156 Scm -1 i.e. in the 54.6% propilen carbonate with 40% NH 4 Cl and PVA . The lowest value was 0.009 Scm -1 i.e. in the NH 4 SCN based electrolyte without propilene carbonate and electronic conductivity showed that the highest value was 0.0156 Scm -1 i.e. 40% NH 4 Cl-PVA and NH 4 SCN-PVA and the lowest value was 0.009 Scm -1 , i.e. in the NH 4 SCN based electrolyte without propilene carbonate. Factorial analyses showed that the concentrations of electrolyte and the plasticizer affect conductivity value. FTIR (Fourier Transform Infrared) measurement showed that the addition of propilene carbonate did not show new bond formation between electrolyte and PVA. It can be shown in absence of characteristic wave number for propilene carbonate and NH 4 + ion. Keywords: DOE, plasticizer, propylenecarbonate, ionic, electronic, conductivity

Multivariate Curve Resolution and Carbon Balance Constraint to Unravel FTIR Spectra from Fed-Batch Fermentation Samples.

The current work investigates the capability of a tailored multivariate curve resolution–alternating least squares (MCR-ALS) algorithm to analyse glucose, phosphate, ammonium and acetate dynamics simultaneously in an E. coli BL21 fed-batch fermentation. The high-cell-density (HCDC) process is monitored by ex situ online attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopy and several in situ online process sensors. This approach efficiently utilises automatically generated process data to reduce the time and cost consuming reference measurement effort for multivariate calibration. To determine metabolite concentrations with accuracies between ±0.19 and ±0.96·gL−l, the presented utilisation needs primarily—besides online sensor measurements—single FTIR measurements for each of the components of interest. The ambiguities in alternating least squares solutions for concentration estimation are reduced by the insertion of analytical process knowledge primarily in the form of elementary carbon mass balances. Thus, in this way, the established idea of mass balance constraints in MCR combines with the consistency check of measured data by carbon balances, as commonly applied in bioprocess engineering. The constraints are calculated based on online process data and theoretical assumptions. This increased calculation effort is able to replace, to a large extent, the need for manually conducted quantitative chemical analysis, leads to good estimations of concentration profiles and a better process understanding.

Biofabrication of size controllable silver nanoparticles – A green approach

A facile biosynthetic approach for the size controllable production of silver nanoparticles (AgNPs) using the leaf extract of Cinnamomum tsoi as reducing and capping agent is developed. The polyphenolic functionalities present in the extract are essentially responsible for the synthesis and stabilization of AgNPs. The size and morphology of the AgNPs were effectively tuned by changing the volume of the extract. The availability of oxidized polyphenols play key role in tuning the size and morphology of the prepared NPs. The as prepared AgNPs were characterized by X-ray diffraction (XRD), Ultraviolet–visible spectroscopy (UV–visible), Transmission electron microscopy (TEM), Selected area electron diffraction (SAED), Dynamic light scattering (DLS) and Fourier transform infrared (FTIR) techniques. FTIR and Zeta potential measurements have confirmed the decoration of oxidized polyphenols on the surface of synthesized AgNPs. TEM and DLS measurements revealed the size variation of AgNPs with change in the volume of plant extract. The prepared AgNPs showed the significant inhibition of α-amylase and α-glucosidase enzymes and exhibited a dose dependent activity. The enhanced in-vitro antidiabetic activity of the AgNPs may be due to the oxidized polyphenols present on the AgNPs surface which was confirmed by FTIR analysis. In addition, the present method is substitute to the chemical approaches of size controlled AgNPs synthesis that are being used nowadays.

Competition between Al2O3 atomic layer etching and AlF3 atomic layer deposition using sequential exposures of trimethylaluminum and hydrogen fluoride.

The thermal atomic layer etching (ALE) of Al2O3 can be performed using sequential and self-limiting reactions with trimethylaluminum (TMA) and hydrogen fluoride (HF) as the reactants. The atomic layer deposition (ALD) of AlF3 can also be accomplished using the same reactants. This paper examined the competition between Al2O3 ALE and AlF3 ALD using in situ Fourier transform infrared (FTIR) vibrational spectroscopy measurements on Al2O3 ALD-coated SiO2 nanoparticles. The FTIR spectra could observe an absorbance loss of the Al-O stretching vibrations during Al2O3 ALE or an absorbance gain of the Al-F stretching vibrations during AlF3 ALD. The transition from AlF3 ALD to Al2O3 ALE occurred versus reaction temperature and was also influenced by the N2 or He background gas pressure. Higher temperatures and lower background gas pressures led to Al2O3 ALE. Lower temperatures and higher background gas pressures led to AlF3 ALD. The FTIR measurements also monitored AlCH3* and HF* species on the surface after the TMA and HF reactant exposures. The loss of AlCH3* and HF* species at higher temperatures is believed to play a vital role in the transition between AlF3 ALD at lower temperatures and Al2O3 ALE at higher temperatures. The change between AlF3 ALD and Al2O3 ALE was defined by the transition temperature. Higher transition temperatures were observed using larger N2 or He background gas pressures. This correlation was associated with variations in the N2 or He gas thermal conductivity versus pressure. The fluorination reaction during Al2O3 ALE is very exothermic and leads to temperature rises in the SiO2 nanoparticles. These temperature transients influence the Al2O3 etching. The higher N2 and He gas thermal conductivities are able to cool the SiO2 nanoparticles more efficiently and minimize the size of the temperature rises. The competition between Al2O3 ALE and AlF3 ALD using TMA and HF illustrates the interplay between etching and growth and the importance of substrate temperature. Background gas pressure also plays a key role in determining the transition temperature for nanoparticle substrates.

Fourier Transform Infrared Spectroscopy Measurements of Multi-phonon and Free-Carrier Absorption in ZnO

Fourier transform infrared (FTIR) measurements were carried out on thin films and bulk single crystals of ZnO over a wide temperature range to study the free-carrier and multi-phonon infrared absorptions and the effects of hydrogen incorporation on these properties. Aluminum-doped ZnO thin films were deposited on quartz substrates using atomic-layer deposition (ALD) and sol–gel methods. Hall-effect measurements showed that the ALD films have a resistivity of ρ = 1.11 × 10−3 Ω cm, three orders of magnitude lower than sol–gel films (ρ = 1.25 Ω cm). This result is consistent with the significant difference in their free-carrier absorption as revealed by FTIR spectra obtained at room temperature. By reducing the temperature to 80 K, the free carriers were frozen out, and their absorption spectrum was suppressed. From the FTIR measurements on ZnO single crystals that were grown by the chemical vapor transport method, we identified a shoulder around 3350 cm−1 and associated it with the presence of two or more hydrogen ions in a Zn vacancy. After reducing the hydrogen level in the crystal, the measurements revealed the multi-phonon absorption of ZnO in the range of 700–1200 cm−1. This study shows that the multi-phonon absorption bands can be completely masked by the presence of a large concentration of hydrogen in the crystals.

The Zugspitze radiative closure experiment for quantifying water vapor absorption over the terrestrial and solar infrared – Part 1: Setup, uncertainty analysis, and assessment of far-infrared water vapor continuum

Abstract. Quantitative knowledge of water vapor radiative processes in the atmosphere throughout the terrestrial and solar infrared spectrum is still incomplete even though this is crucial input to the radiation codes forming the core of both remote sensing methods and climate simulations. Beside laboratory spectroscopy, ground-based remote sensing field studies in the context of so-called radiative closure experiments are a powerful approach because this is the only way to quantify water absorption under cold atmospheric conditions. For this purpose, we have set up at the Zugspitze (47.42° N, 10.98° E; 2964 m a.s.l.) a long-term radiative closure experiment designed to cover the infrared spectrum between 400 and 7800 cm−1 (1.28–25 µm). As a benefit for such experiments, the atmospheric states at the Zugspitze frequently comprise very low integrated water vapor (IWV; minimum = 0.1 mm, median = 2.3 mm) and very low aerosol optical depth (AOD = 0.0024–0.0032 at 7800 cm−1 at air mass 1). All instruments for radiance measurements and atmospheric-state measurements are described along with their measurement uncertainties. Based on all parameter uncertainties and the corresponding radiance Jacobians, a systematic residual radiance uncertainty budget has been set up to characterize the sensitivity of the radiative closure over the whole infrared spectral range. The dominant uncertainty contribution in the spectral windows used for far-infrared (FIR) continuum quantification is from IWV uncertainties, while T profile uncertainties dominate in the mid-infrared (MIR). Uncertainty contributions to near-infrared (NIR) radiance residuals are dominated by water vapor line parameters in the vicinity of the strong water vapor bands. The window regions in between these bands are dominated by solar Fourier transform infrared (FTIR) calibration uncertainties at low NIR wavenumbers, while uncertainties due to AOD become an increasing and dominant contribution towards higher NIR wavenumbers. Exceptions are methane or nitrous oxide bands in the NIR, where the associated line parameter uncertainties dominate the overall uncertainty. As a first demonstration of the Zugspitze closure experiment, a water vapor continuum quantification in the FIR spectral region (400–580 cm−1) has been performed. The resulting FIR foreign-continuum coefficients are consistent with the MT_CKD 2.5.2 continuum model and also agree with the most recent atmospheric closure study carried out in Antarctica. Results from the first determination of the NIR water vapor continuum in a field experiment are detailed in a companion paper (Reichert and Sussmann, 2016) while a novel NIR calibration scheme for the underlying FTIR measurements of incoming solar radiance is presented in another companion paper (Reichert et al., 2016).

Seasonal variability of surface and column carbon monoxide over the megacity Paris, high-altitude Jungfraujoch and Southern Hemispheric Wollongong stations

Abstract. This paper studies the seasonal variation of surface and column CO at three different sites (Paris, Jungfraujoch and Wollongong), with an emphasis on establishing a link between the CO vertical distribution and the nature of CO emission sources. We find the first evidence of a time lag between surface and free tropospheric CO seasonal variations in the Northern Hemisphere. The CO seasonal variability obtained from the total columns and free tropospheric partial columns shows a maximum around March–April and a minimum around September–October in the Northern Hemisphere (Paris and Jungfraujoch). In the Southern Hemisphere (Wollongong) this seasonal variability is shifted by about 6 months. Satellite observations by the IASI–MetOp (Infrared Atmospheric Sounding Interferometer) and MOPITT (Measurements Of Pollution In The Troposphere) instruments confirm this seasonality. Ground-based FTIR (Fourier transform infrared) measurements provide useful complementary information due to good sensitivity in the boundary layer. In situ surface measurements of CO volume mixing ratios at the Paris and Jungfraujoch sites reveal a time lag of the near-surface seasonal variability of about 2 months with respect to the total column variability at the same sites. The chemical transport model GEOS-Chem (Goddard Earth Observing System chemical transport model) is employed to interpret our observations. GEOS-Chem sensitivity runs identify the emission sources influencing the seasonal variation of CO. At both Paris and Jungfraujoch, the surface seasonality is mainly driven by anthropogenic emissions, while the total column seasonality is also controlled by air masses transported from distant sources. At Wollongong, where the CO seasonality is mainly affected by biomass burning, no time shift is observed between surface measurements and total column data.

Quantification of bovine milk protein composition and coagulation properties using infrared spectroscopy and chemometrics: A result of collinearity among reference variables.

Predicting protein fractions and coagulation properties in bovine milk using Fourier transform infrared (FT-IR) measurements is desirable. However, such predictions may rely on correlations with total protein content. The aim of this study was to show how correlations between total protein content, protein fractions, and coagulation properties are responsible for the successful prediction of protein fractions and rennet-induced coagulation properties in milk samples. This study comprised 832 bovine milk samples from 2 breeds (426 Holstein and 406 Jersey). Holstein samples were collected from 20 Danish dairy herds from October to December 2009; Jersey samples were collected from 22 Danish dairy herds from February to April 2010. All samples were from conventional herds and taken while cows were housed. The results showed that κ-CN, αS1-CN, αS1-CN with 8 phosphorylated groups attached (αS1-CN 8P), and curd firming rate could be predicted from FT-IR measurements of the milk samples (with coefficients of determination between 0.66 and 0.71). However, the success of these FT-IR-based predictions was based on indirect relationships with total protein content. Hence, the FT-IR predictions relied on covariance structures with total protein content rather than absorption bands directly associated with the protein fractions and coagulation properties. If covariance structures between the protein fractions, coagulation properties, and total protein content used to calibrate partial least squares models were not conserved in future samples, these samples would show incorrect predictions of the protein fractions and coagulation properties. We demonstrated this using samples from 1 breed to calibrate and samples from the other breed to validate partial least squares models for β-CN. The 2 breeds had different covariance structures between β-CN and total protein content, and the validation samples yielded incorrect predictions. This finding may limit the usefulness of FT-IR-based predictions of protein fractions in milk recording, because indirect covariance structures in the calibration set must be valid for future samples, or future samples will show incorrect predictions.

Biosynthesis and Biomedical Applications of Gold Nanoparticles Using Eclipta prostrata Leaf Extract

This study reports the biological synthesis of gold nanoparticles (AuNPs) by the reduction of HAuCl4 by using of Eclipta prostrata leaf extract as the reducing and stabilizing agent. AuNPs were characterized using Ultraviolet–visible (UV-vis) spectroscopy, X-ray diffraction (XRD), Fourier Transform-Infrared (FTIR) spectroscopy, Scanning Electron Microscopy (SEM), High Resolution-Transmission Electron Microscopy (HRTEM), and Energy Dispersive X-ray analysis (EDAX). The UV-visible spectrum of the synthesized AuNPs showed surface plasmon resonance (SPR) around 534 nm. The face-centered cubic (FCC) structure of the AuNPs was confirmed by XRD peaks at 38.10°, 44.13°, 64.43°, and 77.32°, which correspond to (111), (200), (220), and (311) miller indices, respectively, with clear circular spots in the selected area electron diffraction (SAED). FTIR measurements showed the AuNPs having a coating of phenolic compounds, indicating a possible role of biomolecules responsible for capping and efficient stabilization of the AuNPs. The HRTEM images determined the particles are spherical, hexagonal, and triangular in shape, with an average size of 31 ± 1.6 nm. The synthesized AuNPs show good antibacterial, antioxidant, and cytotoxic activity. The outcomes of this study indicate that these nanoparticles could be effectively utilized in pharmaceutical, biotechnological, and biomedical applications.

Intercomparison of in situ NDIR and column FTIR measurements of CO<sub>2</sub> at Jungfraujoch

Abstract. We compare two CO2 time series measured at the High Alpine Research Station Jungfraujoch, Switzerland (3580 m a.s.l.), in the period from 2005 to 2013 with an in situ surface measurement system using a nondispersive infrared analyzer (NDIR) and a ground-based remote sensing system using solar absorption Fourier transform infrared (FTIR) spectrometry. Although the two data sets show an absolute shift of about 13 ppm, the slopes of the annual CO2 increase are in good agreement within their uncertainties. They are 2.04 ± 0.07 and 1.97 ± 0.05 ppm yr−1 for the FTIR and the NDIR systems, respectively. The seasonality of the FTIR and the NDIR systems is 4.46 ± 1.11 and 10.10 ± 0.73 ppm, respectively. The difference is caused by a dampening of the CO2 signal with increasing altitude due to mixing processes. Whereas the minima of both data series occur in the middle of August, the maxima of the two data sets differ by about 10 weeks; the maximum of the FTIR measurements is in the middle of January, and the maximum of the NDIR measurements is found at the end of March. Sensitivity analyses revealed that the air masses measured by the NDIR system at the surface of Jungfraujoch are mainly influenced by central Europe, whereas the air masses measured by the FTIR system in the column above Jungfraujoch are influenced by regions as far west as the Caribbean and the USA.The correlation between the hourly averaged CO2 values of the NDIR system and the individual FTIR CO2 measurements is 0.820, which is very encouraging given the largely different sampling volumes. Further correlation analyses showed, that the correlation is mainly driven by the annual CO2 increase and to a lesser degree by the seasonality. Both systems are suitable to monitor the long-term CO2 increase, because this signal is represented in the whole atmosphere due to mixing.

Stoichiometry and structural studies of Fe(III) and Zn(II) solvent extraction using D2EHPA/TBP

Abstract The extraction equilibrium of Zn(II) and Fe(III) from chloride solution by the mixture of TBP (tri-n-butyl phosphate) and D2EHPA (di(2-ethylhexyl) phosphoric acid), diluted in kerosene was studied. The results show that in TBP to D2EHPA volume ratio of 3:1 (0.55 M TBP:0.15 M D2EHPA) ΔpH0.5 increased to about 2.5 and Fe(III) and Zn(II) extracted separately with the percentage extraction of 99% and 80%, respectively. The Fourier transform infrared (FTIR) measurements were used in order to find the possible structural functionalities of extracted species in the organic phase. Moreover, the FTIR measurements indicated that there was a hydrogen bond between TBP and D2EHPA molecules. According to FTIR studies and slope analysis method, the reaction between TBP, D2EHPA and zinc was determined and the FTIR-ATR (attenuated total reflectance) method was also employed to verify the stoichiometry of Zn(II) - organic complexes in the organic phase. Both FTIR-ATR and slope analysis methods provided the same results that the ZnA2AH·TBP was probably the extracted specie in the organic phase.

Role of nickel ion coordination on spectroscopic properties of multi-component CaF2–Bi2O3–P2O5–B2O3 glass-ceramics

Multi-component CaF2–Bi2O3–P2O5–B2O3 glasses doped with different concentrations of NiO were crystallized through heat treatment. The prepared glass ceramic samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), differential thermal analysis (DTA) as well as conventional spectroscopic studies viz., optical absorption, Fourier transform infrared (FTIR) and Raman. The XRD and SEM studies have indicated that the samples contain well defined and randomly distributed grains of different crystalline phases. The optical absorption studies together with FTIR and Raman measurements indicated the gradual transformation of nickel ions from tetrahedral sites to octahedral sites (lasing sites) as the concentration of NiO is increased beyond 1.5 mol%. All these investigations have indicated that the growing degree of disorder in the glass ceramic network at higher concentrations of NiO. Glass ceramics doped with NiO beyond 1.5 mol% appear to be suitable for getting laser emission due to 3T2(F) → 3A2(F) transition in NIR region. These glass-ceramics can be expected as an amplification medium for tunable lasers and broadband optical amplifiers for wavelength division multiplexing transmission system.

Mesoporous polyaniline nanofiber decorated graphene micro-flowers for enzyme-less cholesterol biosensors

In the present work, we have studied a nanocomposite of polyaniline nanofiber-graphene microflowers (PANInf-GMF), prepared by an in situ rapid mixing polymerization method. The structural and morphological studies of the nanocomposite (PANInf-GMF) were carried out by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared (FTIR) and Raman spectroscopy. The mesoporous, nanofibrous and microflower structures were observed by scanning electron microscopy. The functional groups and synergetic effects were observed by FTIR and micro-Raman measurements. The water wettability was carried out by a contact angle measurement technique and found to be super hydrophilic in nature towards water. This nanocomposite was deposited onto indium-tin-oxide coated glass substrate by a drop casting method and used for the detection of cholesterol using an electrochemical technique. The differential pulse voltammetry studies show the appreciable increase in the current with the addition of 1.93 to 464.04 mg dl−1 cholesterol concentration. It is also found that the electrodes were highly selective towards cholesterol when compared to other biological interfering analytes, such as glucose, urea, citric acid, cysteine and ascorbic acid. The sensitivity of the sensor is estimated as 0.101 μA mg−1 dl cm−2 and the lower detection limit as 1.93 mg dl−1. This work will throw light on the preparation of non-enzymatic biosensors based on PANInf-carbon nanostructure composites.

Monocyclic monoterpenes as penetration enhancers of ligustrazine hydrochloride for dermal delivery

The purpose of this study was to explore the enhancing effects and the mechanism of monocyclic monoterpene penetration enhancers (menthol and menthone) on the transdermal absorption of ligustrazine hydrochloride (LH). Franz-type diffusion cells were used to determine percutaneous parameters of LH in vitro and surface changes of porcine skin were studied by a scanning electron microscope (SEM). The effects of promoters on the biophysical natures of stratum corneum (SC) were researched by Fourier transform-infrared (FT-IR). Penetration parameters of menthol (p < 0.01) and menthone groups (p < 0.05) were greater than those of the control; morphological changes of skin monitored by SEM demonstrated that the menthone group had the most disruption and desquamation of SC flakes, which resulted from extracted lipids. FT-IR measurements showed menthone had the greatest changes in peak shift and peak area, which resulted from C–H stretching vibrations of SC lipids. The results suggest that the penetration mechanism might include disturbing and extracting SC lipids and the hydrogen bond connection.

LLDPE films containing monoester of oleic acid grafted to silica particles as durable antifog additives

Antifog additives (AF) are incorporated into polymeric systems to improve their wettability. When added to a polyethylene (PE) film, the AF molecules migrate to the films' surface and their concentration decreases; over time the additive's effect desists. Extended additives' performance is necessary to avoid frequent substitution of PE films for different applications (e.g. greenhouses coverings), as a result, reducing plastics' waste and contributing to environmental sustainability.This paper presents a simple, low cost, one‐step reaction to create durable AF for PE films, as well as a thorough study of AF migration rate, fog activity, and film properties. Films are prepared by compression‐molding (laboratory scale) and cast‐extrusion (pilot scale). FTIR (Fourier Transform IR) and TGA (Thermal Gravimetric Analysis) measurements confirm the existence of AF grafted particles. Aging tests depict a significant decrease of the AF migration rate. An evaluation test procedure for AF performance shows an extended duration of the AF's activity; the cast‐extrusion films exhibit improved AF durability, compared with the compression‐molded films. Copyright © 2016 John Wiley &amp; Sons, Ltd.