Fourier transform infrared microspectroscopy as a tool to identify macroalgal propagules

Understanding of macroalgal dispersal has been hindered by the difficulty in identifying propagules. Different carrageenans typically occur in gametophytes and tetrasporophytes of the red algal family Gigartinaceae, and we may expect that carpospores and tetraspores also differ in composition of carrageenans. Using Fourier transform infrared (FT-IR) microspectroscopy, we tested the model that differences in carrageenans and other cellular constituents between nuclear phases should allow us to discriminate carpospores and tetraspores of Chondrus verrucosus Mikami. Spectral data suggest that carposporophytes isolated from the pericarp and female gametophytes contained κ-carrageenan, whereas tetrasporophytes contained λ-carrageenan. However, both carpospores and tetraspores exhibited absorbances in wave bands characteristic of κ-,ι-, and λ-carrageenans. Carpospores contained more proteins and may be more photosynthetically active than tetraspores, which contained more lipid reserves. We draw analogies to planktotrophic and lecithotrophic larvae. These differences in cellular chemistry allowed reliable discrimination of spores, but pretreatment of spectral data affected the accuracy of classification. The best classification of spores was achieved with extended multiplicative signal correction (EMSC) pretreatment using partial least squares discrimination analysis, with correct classification of 86% of carpospores and 83% of tetraspores. Classification may be further improved by using synchrotron FT-IR microspectroscopy because of its inherently higher signal-to-noise ratio compared with microspectroscopy using conventional sources of IR. This study demonstrates that FT-IR microspectroscopy and bioinformatics are useful tools to advance our understanding of algal dispersal ecology through discrimination of morphologically similar propagules both within and potentially between species.

Quantitative determination of fatty acid compositions in micro-encapsulated fish-oil supplements using Fourier transform infrared (FTIR) spectroscopy

The research describes a rapid method for the determination of fatty acid (FA) contents in a micro-encapsulated fish-oil (μEFO) supplement by using attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopic technique and partial least square regression (PLSR) analysis. Using the ATR-FTIR technique, the μEFO powder samples can be directly analysed without any pre-treatment required, and our developed PLSR strategic approach based on the acquired spectral data led to production of a good linear calibration with R^₂ = 0.99. In addition, the subsequent predictions acquired from an independent validation set for the target FA compositions (i.e., total oil, total omega-3 fatty acids, EPA and DHA) were highly accurate when compared to the actual values obtained from standard GC-based technique, with plots between predicted versus actual values resulting in excellent linear fitting (R² ⩾ 0.96) in all cases. The study therefore demonstrated not only the substantial advantage of the ATR-FTIR technique in terms of rapidness and cost effectiveness, but also its potential application as a rapid, potentially automated, online monitoring technique for the routine analysis of FA composition in industrial processes when used together with the multivariate.

Attenuated total reflectance fourier transform infrared spectroscopy: an analytical technique to understand therapeutic responses at the molecular level

Rapid monitoring of the response to treatment in cancer patients is essential to predict the outcome of the therapeutic regimen early in the course of the treatment. The conventional methods are laborious, time-consuming, subjective and lack the ability to study different biomolecules and their interactions, simultaneously. Since; mechanisms of cancer and its response to therapy is dependent on molecular interactions and not on single biomolecules, an assay capable of studying molecular interactions as a whole, is preferred. Fourier Transform Infrared (FTIR) spectroscopy has become a popular technique in the field of cancer therapy with an ability to elucidate molecular interactions. The aim of this study, was to explore the utility of the FTIR technique along with multivariate analysis to understand whether the method has the resolution to identify the differences in the mechanism of therapeutic response. Towards achieving the aim, we utilized the mouse xenograft model of retinoblastoma and nanoparticle mediated targeted therapy. The results indicate that the mechanism underlying the response differed between the treated and untreated group which can be elucidated by unique spectral signatures generated by each group. The study establishes the efficiency of non-invasive, label-free and rapid FTIR method in assessing the interactions of nanoparticles with cellular macromolecules towards monitoring the response to cancer therapeutics.

Determination of cashmere and wool fibre scale frequency by analysing diameter profiles with fast fourier transform

This paper describes a potentially faster and cheaper method of determining fibre scale frequencies. The method uses the single fibre analyser (SIFAN) to  determine the along the fibre diameter profile. This information is then analysed by the Fast Fourier Transform technique using computer software. The paper shows the close association between the mean scale frequencies determined by this method and the traditional approach using SEM.

Frictional behaviour and wear performance of a nitrocarburised coating sliding against AISI 1019 steel

This work employed a commercial nitrocaburising process to diffuse a coating onto M2 grade high speed tool steel. Properties of the nitrocaburised coating (CN) such as thickness, roughness and hardness were characterised using a variety of techniques including Glow-Discharge Optical Emission Spectrometry (GD-OES) and Scanning Electron Microscopy (SEM). A tribological test has been developed in which two nominally identical crossed cylinders slide over each other under selected test conditions. The test has been employed to investigate the wear performance of both CN coated and uncoated M2 specimens and frictional behaviour of the sliding interface between the tool and a AISI 1019 steel workpiece under unlubricated (dry) and lubricated conditions. Fourier Transform Infrared Spectroscopy (FTIR) was used to monitor the formation of chemical species from the oxidation of lubricant during tribological testing.

An investigation of tribological properties of CN and TiCN coatings

Today the tool industry on a worldwide basis uses hard, wear-resistant, and low-friction coatings produced by different processes such as electrochemical or electroless methods, spray technologies, thermochemical, chemical-vapor deposition (CVD), and physical vapor deposition (PVD). In the current work, two different coatings, nitrocarburized (CN) and titanium carbonitride (TiCN) on M2-grade tool steel, were prepared by commercial diffusion and PVD techniques, respectively. Properties such as thickness, roughness, and hardness were characterized using a variety of techniques, including glow-discharge optical emission spectrometry (GD-OES) and scanning electron microscopy (SEM). A crossed-cylinders wear-testing machine was used to investigate the performances of both coatings under lubrication. The effect of coatings on the performance of lubricants under a range of wear-test conditions was also examined. Degradation of lubricants during tribological testing was explored by Fourier transform infrared (FTIR) spectroscopy.

Investigation of failure mechanisms in aged aerospace composites

The effect of isothermal ageing on two high temperature, bismaleimide composite materials, a novel CSIRO CBR 320/328 composite and a commercial CIBA GEIGY Matrimid® 5292 composite, was examined at 204 and 250 °C. Delamination is a major cause of failure in composite materials, therefore, the Mode I interlaminar fracture toughness (GIC) of both materials was measured using the double cantilever beam (DCB) test. Chemical degradation of the matrix was monitored concurrently using Fourier transform infrared (FTIR) and Raman spectroscopy. Chemical changes at the core of both of these materials were found to occur concomitantly with the observed changes in interlaminar fracture toughness. FTIR analysis of both matrix materials revealed the predominant degradation mechanism to be the oxidation of the methylene group bridging two aromatic rings common to the structure of both resins, and was substantiated by the ingrowth of a broad peak centred at 1600 cm⁻¹ . In addition to this, the pyromellitic anhydride unit present only in the CBR 320/328 composites was found to be highly resistant to the effects of ageing, whereas the saturated imide, common to the cured structures of both materials, was observed to degrade. Raman spectroscopy indicated that the predominant degradation mechanism of the composites differed at the two ageing temperatures.

Miscibility, crystallization κinetics and real-time small-Angle x-ray scattering investigation of the semicrystalline morphology in thermosetting polymer blends of epoxy resin and poly(ethylene oxide)

Thermosetting polymer blends of poly(ethylene oxide) (PEO) and bisphenol-A-type epoxy resin (ER) were prepared using 4,4′-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA) as curing agent. The miscibility and crystallization behavior of MCDEA-cured ER/PEO blends were investigated by differential scanning calorimetry (DSC). The existence of a single composition-dependent glass transition temperature (Tg) indicates that PEO is completely miscible with MCDEA-cured ER in the melt and in the amorphous state over the entire composition range. Fourier-transform infrared (FTIR) investigations indicated hydrogen-bonding interaction between the hydroxyl groups of MCDEA-cured ER and the ether oxygens of PEO in the blends, which is an important driving force for the miscibility of the blends. The average strength of the hydrogen bond in the cured ER/PEO blends is higher than in the pure MCDEA-cured ER. Crystallization kinetics of PEO from the melt is strongly influenced by the blend composition and the crystallization temperature. At high conversion, the time dependence of the relative degree of crystallinity deviated from the Avrami equation. The addition of a non-crystallizable ER component into PEO causes a depression of both the overall crystallization rate and the melting temperature. The surface free energy of folding σe displays a minimum with variation of composition. The spherulitic morphology of PEO in the ER/PEO blends exhibits typical characteristics of miscible crystalline/amorphous blends, and the PEO spherulites in the blends are always completely volume-filling. Real-time small-angle X-ray scattering (SAXS) experiments reveal that the long period L increases drastically with increasing ER content at the same temperatures. The amorphous cured ER component segregates interlamellarly during the crystallization process of PEO because of the low chain mobility of the cured ER. A model describing the semicrystalline morphology of MCDEA-cured ER/PEO blends is proposed based on the SAXS results. The semicrystalline morphology is a stack of crystalline lamellae; the amorphous fraction of PEO, the branched ER chains and imperfect ER network are located between PEO lamellae.

FTIR and thermal analysis of cashmere and other animal fibres

In this paper, sereval varieties of animal fibres including cashmere and Australian fine Merino wool have been analysed by Fourier transform infrared microscope and differential scanning calorimeter. The results showed that both Chinese and Australian cashmere fibres started absorbing heat at a relatively higher temperature but were thermally degraded quicker than other animal fibres tested. However, the mass changes (within the temperature range of 200oC to 350oC) and associated onset temperatures varied among fibre varieties. From the attenuated total reflectance spectra, the Chinese cashmere was clearly different from Australian cashmere and wool in a peak near 1040 cm-1 wavelength for S-O stretching of cysteic acid residues. The Chinese cashmere presented a stronger absorption at 1019 cm-1 wavelength, while Australian cashmere and wool peaked at 1079 cm-1 wavelength and had a weaker absorption. Combined with thermal analysis, the normalised R-SO3 - content of cysteic acid residues to the amide II peak of the protein backbone may have potential use in identifying Australian fine Merino wool from Chinese cashmere.

Manufacturing process effects on the mode I interlaminar fracture toughness and nanocreep properties of CFRP

Quickstep ™ is a fluid filled floating mould technology which was recently developed by an Australian company of the same name. The Quickstep and conventional autoclave manufacture of composites were compared by investigating the mode I interlaminar fracture toughness and nanocreep propeties of HexPly914 carbon epoxy composites. It was found that composites cured using the Quickstep technology had significantly higher fracture toughness (1.8 times) than the composites cured via autoclave for this system. DMTA (dynamic mechanical thermal analysis) results showed a higher Tg (glass transition temperature) for the material manufactured by the Quickstep than that cured by the autoclave. FTIR (Fourier transform infrared spectroscopy) spectra did not indicate any difference in cure chemistry between the two processes. Nanocreep experiments were performed to explore the viscoelastic properties of the epoxy matrix of composites. The KelvinVoigt three-element model was applied to analyse the indentation creep behaviour of both composites.

Consistent model predictions for isothermal cure kinetics investigation of high performance epoxy prepregs

An accurate kinetics model is essential for understanding the curing mechanism and predicting the end properties of polymer materials. Graphite/epoxy AS4/ 8552 prepreg is a recent high-performance thermosetting composite modified with thermoplastic, which is being used in the manufacture of aircraft and military structures. The isothermal cures of this system along with another thermoplastic toughened high-performance prepreg, the T800H/3900-2 system, were investigated by real-time Fourier transform infrared (FTIR) spectroscopy. The cure rate was quantitatively analyzed based on the concentration profiles of both the epoxy and primary amine groups. Three autocatalytic models were used to determine kinetics parameters for both composite systems. The model which utilizes an empirical term, the final relative conversion (at different isothermal curing temperatures), describes the experimental data of both systems more satisfactorily than the model which applies a diffusion factor. The modeling results suggest that the curing of epoxy within both prepregs can be assumed to be a second order process.

Selective hydrogen bonding and hierarchical nanostructures in poly(hydroxyether of bisphenol A)/poly(ε-caprolactone)-block-poly(2-vinyl pyridine) blends

The phase behavior, hydrogen bonding interactions and morphology of poly(hydroxyether of bisphenol A) (phenoxy) and poly(var epsilon-caprolactone)-block-poly(2-vinyl pyridine) (PCL-b-P2VP) were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy and atomic force microscopy (AFM). In this A-b-B/C type block copolymer/homopolymer system, both P2VP and PCL blocks have favorable intermolecular interaction towards phenoxy via hydrogen bonding. However, the hydrogen bonding between P2VP and phenoxy is significantly stronger than that between PCL and phenoxy. Selective hydrogen bonding between phenoxy/P2VP pair at lower phenoxy contents and co-existence of two competitive hydrogen bonding interactions between phenoxy/P2VP and phenoxy/PCL pairs at higher phenoxy contents were observed in the blends. This leads to the formation of a variety of composition dependent nanostructures including wormlike, hierarchical and core–shell morphologies. The blends became homogeneous at 95 wt% phenoxy where both blocks of the PCL-b-P2VP were miscible with phenoxy due to hydrogen bonding. In the end, a model was proposed to explain the microphase morphology of blends based on the experimental results obtained. The swelling of the PCL-b-P2VP block copolymer by phenoxy due to selective hydrogen bonding causes formation of different microphases

Self-assembled complexes of poly(4-vinylphenol) and poly(ε-caprolactone)-block-poly(2-vinylpyridine) via competitive hydrogen bonding

Nanostructured complexes were prepared from poly(ε-caprolactone)-block-poly(2-vinylpyridine) (PCL-b-P2VP) and poly(4-vinylphenol) (PVPh) in tetrahydrofuran (THF). The phase behavior, specific interactions, and morphology were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). In this A-b-B/C type block copolymer/homopolymer system, both blocks of the PCL-b-P2VP block copolymer have favorable intermolecular interaction toward PVPh via hydrogen bonding, but the interaction between P2VP block and PVPh is significantly stronger than that between PCL block and PVPh. It was found that the disparity in competitive intermolecular interactions, specifically PVPh and P2VP block interact strongly whereas PVPh and PCL block interact weakly, leads to the formation of a variety of nanostructures depending on PVPh concentration. Spherical micelles of 30−40 nm in diameter were obtained in the complex with 10 wt % PVPh, followed by wormlike micelles with size in the order of 40−50 nm in the complexes with 30−60 wt % PVPh. At low PVPh concentrations, PCL interacts weakly with PVPh, whereas in the complexes containing more than 20 wt % PVPh, the PCL block began to interact considerably with PVPh, leading to the formation of composition-dependent nanostructures. The complex becomes homogeneous with PVPh content beyond 60 wt %, since a sufficient amount of PVPh is available to form hydrogen bonds with both PCL and P2VP. Finally, a model was proposed to explain the self-assembly and microphase morphology of these complexes based on the experimental results obtained. The competitive hydrogen-bonding interactions cause the self-assembly and formation of different microphase morphologies.