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.

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.

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.

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.

Tribology of lubricated nitrocarburised and titanium carbonitride surfaces

In the current work, two different coatings, nitrocarburised (CN) and titanium carbonitride (TiCN) on M2 grade high speed tool steel, were prepared by commercial diffusion and physical vapour deposition (PVD) techniques, respectively. Properties of the coating were characterised using a variety of techniques such as Glow-Discharge Optical Emission Spectrometry (GD-OES) and Scanning Electron Microscopy (SEM). Three non-commercial, oil-based lubricants with simplified formulations were used for this study. A tribological test was developed in which two nominally geometrically-identical crossed cylinders slide over each other under selected test conditions. This test was used to evaluate the effectiveness of a pre-applied lubricant film and a surface coating for various conditions of sliding wear. Engineered surface coatings can significantly improve wear resistance of the tool surface but their sliding wear performances strongly depend on the type of coating and lubricant combination used. These coating-lubricant interactions can also have a very strong effect on the useful life of the lubricant in a tribological system. Better performance of lubricants during the sliding wear testing was achieved hen used with the nitrocarburised (CN) coating. To understand the nature of the interactions and their possible effects on the coating-lubricant system, several surface analysis techniques were used. The molecular level investigation of Fourier Transform Infrared Spectroscopy (FTIR) revealed that oxidative degradation occurred in all used oil-based lubricants during the sliding wear test but the degradation behaviour of oil-based lubricants varied with the coating-lubricant system and the wear conditions. The main differences in the carbonyl oxidation region of the FTIR spectra (1900-1600 cm-1) between different coating-lubricant systems may relate to the effective lifetime of the lubricant during the sliding wear test. Secondary Ion Mass Spectrometry (SIMS) depth profiling shows that the CN coating has the highest lubricant absorbability among the tested tool surfaces. Diffusion of chlorine (C1), hydrogen (H) and oxygen (O) into the surface of subsurface of the tool suggested that strong interactions occurred between lubricant and tool surface during the sliding wear test. The possible effects of the interactions on the performance of whole tribological system are also discussed. The study of Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) indicated that the envelope of hydrocarbons (CmHn) of oil lubricant in the positive TOF-SIMS spectra shifted to lower mass fragment after the sliding wear testing due to the breakage of long-chain hydrocarbons to short-chain ones during the degradation of lubricant. The shift of the mass fragment range of the hydrocarbon (CmHn) envelope caries with the type of both tool surface and lubricant, again confirming that variation in the performance of the tool-lubricant system relates to the changes in surface chemistry due to tribochemical interactions at the tool-lubricant interface under sliding wear conditions. The sliding wear conditions resulted in changes not only in topography of the tool surface due to mechanical interactions, as outlined in Chapter 5, but also in surface chemistry due to tribochemical interactions, as discussed in Chapters 6 and 7.

Dispersion of boron nitride nanotubes in aqueous solution with the help of ionic surfactants

We report that ammonium oleate surfactants can help the dispersion of multiwalled boron nitride nanotubes (BNNTs) in water to form a BNNT solution stable for several months, which was due to the non-covalent functionalization of nanotube surfaces. Fourier Transform Infrared Spectroscopy (FTIR) and Photoluminescence (PL) analysis with synchrotron radiation source revealed that this BNNT aqueous solution preserves the intrinsic optical properties of BNNTs. © 2009 Elsevier Ltd. All rights reserved.

Wool powders used as sorbents to remove Co2+ ions from aqueous solution

The Co2+ sorption of two wool powders was investigated using its radioisotope 57Co (T1/2=271.8 days and γ=122.1 and 136.5 keV) as a tracer. The effects of the type of buffer, the pH value, the contact time and the initial concentration of Co2+ on the sorption behaviour of wool powders were studied. The Co2+ releasing ability of wool powders and the re-use of wool powders to sorb Co2+ were also examined. The optimum sorption of Co2+ by the powders occurred at pH 8 in phosphate buffer and pH 10 in ammonium sulphate buffer. Fourier-transform infrared spectroscopy (FTIR) was used to study the changes in chemical structure of the wool after exposure to both buffer solutions. Compared to the untreated wool fibre, the fine wool powders showed rapid sorption rates and high sorption capacities for Co2+. Co2+ ions were recovered after exposing the Co2+ loaded wool to HCl (0.1 M) and buffer at pH 3 (glycine/sodium chloride). After releasing Co2+ ions from wool powders, the efficiency of wool powders re-used to sorb Co2+ was 80% of that of the fresh wool powders. It is concluded from this study that wool powder can be used as an efficient sorbent to remove and release Co2+ from solution.

Molecular identification of marine yeast and its spectroscopic analysis establishes unsaturated fatty acid accumulation

Marine microbes are competent organisms, some of which can accumulate large amounts of lipids. A yeast strain, Rhodotorula mucilaginosa AMCQ8A was isolated from the marine water of the Queenscliff region, Victoria, Australia. The yeast isolate was identified by sequencing 18s rDNA genes. Scanning electron microscopy images revealed scars on the surface of the yeast cells. The Fourier transform infrared spectroscopy microspectroscopy studies demonstrated the presence of unsaturated fatty acids by differential microscopic analysis. The sharp band at 1745 cm^-1 was represented by ν(C=O) stretches of ester functional groups from lipids and fats, and therefore indicated the presence of total lipids produced by the cells. Over 65% of the fatty acids from the yeast strain were analyzed as C¹⁶ and C^18:1 with omega-3 content from about 6% to 7%. Thus, this marine-derived yeast could be a potential source of lipids, including omega-3 fatty acids. 2012, The Society for Biotechnology, Japan. All rights reserved.

Preparation and characterization of graphitic carbon nitride through pyrolysis of melamine

Graphitic carbon nitride (g-C₃N₄) has been synthesized via a two-step pyrolysis of melamine (C₃H₆N₆) at 800°C for 2 h under vacuum conditions. X-ray diffraction (XRD) patterns strongly indicate that the synthesized sample is g-C₃N₄. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) morphologies indicate that the product is mainly composed of graphitic carbon nitride. The stoichiometric ratio of C:N is determined to be 0.72 by elemental analysis (EA). Chemical bonding of the sample has been investigated by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Electron energy loss spectroscopy (EELS) verifies the bonding state between carbon and nitrogen atoms. Optical properties of the g-C₃N₄ were investigated by PL (photoluminescence) measurements and UV–Vis (ultraviolet–visible) absorption spectra. We suppose its luminescent properties may have potential application as component of optical nanoscale devices. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were also performed.

Polystyrene-b-poly(oligo(ethylene oxide) monomethyl ether methacrylate)-bpolystyrene triblock copolymers as potential carriers for hydrophobic drugs

A simple and effective method is introduced to synthesize a series of polystyrene-b-poly(oligo(ethylene oxide) monomethyl ether methacrylate)-b- polystyrene (PSt-b-POEOMA-b-PSt) triblock copolymers. The structures of PSt-b-POEOMA-b-PSt copolymers were characterized by Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (1H NMR) spectroscopy. The molecular weight and molecular weight distribution of the copolymer were measured by gel permeation chromatography (GPC). Furthermore£ the self-assembling and drug-loaded behaviours of three different ratios of PSt-b-POEOMA-b-PSt were studied. These copolymers could readily self-assemble into micelles in aqueous solution. The vitamin E-loaded copolymer micelles were produced by the dialysis method. The micelle size and core-shell structure of the block copolymer micelles and the drug-loaded micelles were confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The thermal properties of the copolymer micelles before and after drug-loaded were investigated by different scanning calorimetry (DSC). The results show that the micelle size is slightly increased with increasing the content of hydrophobic segments and the micelles are still core-shell spherical structures after drug-loaded. Moreover, the glass transition temperature (Tg) of polystyrene is reduced after the drug loaded. The drug loading content (DLC) of the copolymer micelles is 70%-80% by ultraviolet (UV) photolithography analysis. These properties indicate the micelles self-assembled from PSt-b- POEOMA-b- PSt copolymers would have potential as carriers for the encapsulation of hydrophobic drugs.

Preparation and characterization of natural rubber/silica nanocomposites using rule of similarity in latex

Rule of similarity and latex compounding techniques were combined for the first time to prepare natural rubber/nanosilica (NR/SiO2) nanocomposite with core-shell nanosilica-poly (methyl methacrylate) (SiO 2-PMMA) particles and PMMA-modified natural rubber matrix (NR-PMMA). The microstructure of SiO2 and nanocomposites with different SiO 2 contents was characterized by fourier transform infrared spectroscopy (FTIR); the morphology of nanocomposites was investigated with scanning electron microscopy (SEM); the tensile strength was characterized by tensile testing machine and the thermal stability of composites was studied by thermal gravimetric analysis. Results showed that PMMA chains have successfully grafted onto the surface of SiO2, and the core-shell SiO 2-PMMA nanoparticles and NR-PMMA latex have been perfectly incorporated. SiO2-PMMA nanoparticles are evenly distributed over the NR matrix with an average size in the range of 60-100 nm at the low content (SiO2? 3 wt%), while aggregations are apparently observed when 5 wt% SiO2 is loaded. In addition, NR/SiO2 composities possess a considerable improvement in ageing resistance compared with the pure NR. The tensile strength of composite increases from 6.99 to 12.72 MPa, reaching the highest value at a 0.5 wt% SiO2 loading, and then the figure decreases gradually because of the aggregation of SiO2 nanoparticles. It is anticipated that the reported process is to provide a simple and economic way for preparing NR composites.

Synthesis and biological evaluation of novel folic acid receptor-targeted, β-cyclodextrin-based drug complexes for cancer treatment

Drug targeting is an active area of research and nano-scaled drug delivery systems hold tremendous potential for the treatment of neoplasms. In this study, a novel cyclodextrin (CD)-based nanoparticle drug delivery system has been assembled and characterized for the therapy of folate receptor-positive [FR(+)] cancer. Water-soluble folic acid (FA)-conjugated CD carriers (FACDs) were successfully synthesized and their structures were confirmed by 1D/2D nuclear magnetic resonance (NMR), matrix-assisted laser desorption ionization time-of-flight mass spectrometer (MALDI-TOF-MS), high performance liquid chromatography (HPLC), Fourier transform infrared spectroscopy (FTIR), and circular dichroism. Drug complexes of adamatane (Ada) and cytotoxic doxorubicin (Dox) with FACD were readily obtained by mixed solvent precipitation. The average size of FACD-Ada-Dox was 1.5-2.5 nm. The host-guest association constant Ka was 1,639 M-1 as determined by induced circular dichroism and the hydrophilicity of the FACDs was greatly enhanced compared to unmodified CD. Cellular uptake and FR binding competitive experiments demonstrated an efficient and preferentially targeted delivery of Dox into FR-positive tumor cells and a sustained drug release profile was seen in vitro. The delivery of Dox into FR(+) cancer cells via endocytosis was observed by confocal microscopy and drug uptake of the targeted nanoparticles was 8-fold greater than that of non-targeted drug complexes. Our docking results suggest that FA, FACD and FACD-Ada-Dox could bind human hedgehog interacting protein that contains a FR domain. Mouse cardiomyocytes as well as fibroblast treated with FACD-Ada-Dox had significantly lower levels of reactive oxygen species, with increased content of glutathione and glutathione peroxidase activity, indicating a reduced potential for Dox-induced cardiotoxicity. These results indicate that the targeted drug complex possesses high drug association and sustained drug release properties with good biocompatibility and physiological stability. The novel FA-conjugated β-CD based drug complex might be promising as an anti-tumor treatment for FR(+) cancer.

Isotherm, kinetic, and thermodynamic equations for cefalexin removal from liquids using activated carbon synthesized from loofah sponge

Activated carbon (AC) developed from loofah sponge with phosphoric acid activation was applied to absorb cefalexin (CEX) in aqueous solution. AC was characterized by N2 adsorption–desorption isotherms and Fourier transform infrared spectroscopy (FTIR). Factors influencing the adsorption process were investigated. The equilibrium adsorption isotherms and kinetics of CEX were also studied. The results showed that AC prepared from loofah sponge had rough surface and abundant pores. The determination results of specific surface area (810.12 m²/g) and average pore size (5.28 nm) suggested the high adsorption capability. At low concentration, the AC could adsorb about 95% of CEX. The adsorption effect was independent of the temperature and pH. The maximum adsorption amount of CEX was about 55.11 mg/g at 308 K. The equilibrium data agreed well with Freundlich isotherm equation (R² = 0.9957) at 308 K, which indicated multilayer adsorption. FTIR analysis suggested the existence of phosphorus-containing functional groups, C–O bond, and C=C bond on the surface of AC of which the peak intensity of AC after adsorption was slightly lower after adsorption, indicating that the AC surface groups interacted with or were covered by the CEX species.

Transesterification induced mechanical properties enhancement of PLLA/PHBV bio-alloy

In order to improve the miscibility and mechanical properties of poly(l-lactic acid) (PLLA) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) bio-alloy, small amount of transesterification catalyst, zinc acetate was added in the melt blending process. We show that the PLLA-PHBV copolymer generated during the melt blending significantly improves the miscibility and therefore enhances the mechanical properties of the product. Dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), and tensile tests were performed to study the miscibility and mechanical properties of the blends. Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC) were used to reveal the molecular structural, and molecular weight changes of PLLA and PHBV after melt mixing with zinc acetate. SEM and FTIR results have clearly shown that the PLLA-PHBV copolymer generated from transesterification reaction acted as a compatibilizer and therefore resulted in an improved interfacial miscibility and ductility of PLLA/PHBV blend. In our mechanistic study, a competition between the PLLA/PHBV transesterification reaction and the thermal decomposition of PHBV was identified for the first time. On the basis of these observations, a new mechanism of transesterification reaction was proposed.