Forensic analysis of architectural finishes using Fourier transform infrared and Raman spectroscopy, Part I: The resin bases

The ability of Raman spectroscopy and Fourier transform infrared (FT-IR) microscopy to discriminate between resins used for the manufacture of architectural finishes was examined in a study of 39 samples taken from a commercial resin library. Both Raman and FT-IR were able to discriminate between different types of resin and both split the samples into several groups (six for FT-IR, six for Raman), each of which gave similar, but not identical, spectra. In addition, three resins gave unique Raman spectra (four in FTIR). However, approximately half the library comprised samples that were sufficiently similar that they fell into a single large group, whether classified using FT-IR or Raman, although the remaining samples fell into much smaller groups. Further sub-division of the FT-IR groups was not possible because the experimental uncertainty was of similar magnitude to the within-group variation. In contrast, Raman spectroscopy was able to further discriminate between resins that fell within the same groups because the differences in the relative band intensities of the resins, although small, were larger than the experimental uncertainty.

Forensic analysis of architectural finishes using fourier transform infrared and raman spectroscopy, part II:White paint

White household paints are commonly encountered as evidence in the forensic laboratory but they often cannot be readily distinguished by color alone so Fourier transform infrared (FT-IR) microscopy is used since it can sometimes discriminate between paints prepared with different organic resins. Here we report the first comparative study of FT-IR and Raman spectroscopy for forensic analysis of white paint. Both techniques allowed the 51 white paint samples in the study to be classified by inspection as either belonging to distinct groups or as unique samples. FT-IR gave five groups and four unique samples; Raman gave seven groups and six unique samples. The basis for this discrimination was the type of resin and/ or inorganic pigments/extenders present. Although this allowed approximately half of the white paints to be distinguished by inspection, the other half were all based on a similar resin and did not contain the distinctive modifiers/pigments and extenders that allowed the other samples to be identified. The experimental uncertainty in the relative band intensities measured using FT-IR was similar to the variation within this large group, so no further discrimination was possible. However, the variation in the Raman spectra was larger than the uncertainty, which allowed the large group to be divided into three subgroups and four distinct spectra, based on relative band intensities. The combination of increased discrimination and higher sample throughput means that the Raman method is superior to FT-IR for samples of this type. © 2005 Society for Applied Spectroscopy.

Perturbed frequency-selective surfaces fabricated on large thin polymer membranes for multiband infrared applications

The design, fabrication, and characterization of single-screen perturbed frequency-selective surfaces (FSS) at infrared frequencies for single and multiband applications are reported. Single-band FSS based on parallel strips have been perturbed by decreasing the length of every second strip within the array in order to achieve dual band-stop responses. The same principle has been extended to design FSS exhibiting tri- and quadreflection bands. In addition, strip FSSs have been perturbed by replacing every second strip for a metallic ring, resulting in dual-band filters with different polarization responses of the bands. These designs have been fabricated on large thin polyimide membranes using sacrificial silicon wafers. An oxide interlayer between the sacrificial silicon wafer and the polyimide membrane is employed to stop the silicon etching and is wet etched subsequently by a solution of ammonium fluoride and acetic acid that does not attack either the polyimide membrane or the aluminium FSS elements. Fourier transform infrared spectroscopy measurements are presented to validate the predicted responses of the fabricated prototypes.

Physicochemical Characterization of Poly(ethylene glycol) Plasticized Poly(methyl vinyl ether-co-maleic acid) Films

The influence of the poly(ethylene glycol) (PEG) plasticizer content and molecular weight on the physicochemical properties of films cast from aqueous blends of poly(methyl vinyl ether-co-maleic acid) (PMVE/MA) was investigated with tensile mechanical testing, thermal analysis, and attenuated total reflectance/Fourier transform infrared spectroscopy. Unplasticized films and those containing high copolymer contents were very difficult to handle and proved difficult to test. PEG with a molecular weight of 200 Da was the most efficient plasticizer. However, films cast from aqueous blends containing 10% (w/w) PMVE/MA and either PEG 1000 or PEG 10,000 when the copolymer/plasticizer ratio was 4 : 3 and those cast from aqueous blends containing 15% (w/w) PMVE/MA and either PEG 1000 or PEG 10,000 when the copolymer/plasticizer ratio was 2 : 1 possessed mechanical properties most closely mimicking those of a formulation we have used clinically in photodynamic therapy. Importantly, we found previously that films cast from aqueous blends containing 10% (w/w) PMVE/MA performed rather poorly in the clinical setting, where uptake of moisture from patients' skin led to reversion of the formulation to a thick gel. Consequently, we are now investigating films cast from aqueous blends containing 15% (w/w) PMVE/MA and either PEG 1000 or PEG 10,000, where the copolymer/plasticizer ratio is 2 : 1, as possible Food and Drug Administration approved replacements for our current formulation, which must currently be used only on a named patient basis as its plasticizer, tripropylene glycol methyl ether, is not currently available in pharmaceutical grade

Adsorption mechanisms of removing heavy metals and dyes from aqueous solution using date pits solid adsorbent

A potential usefulness of raw date pits as an inexpensive solid adsorbent for methylene blue (MB), copper ion (Cu2+), and cadmium ion (Cd2+) has been demonstrated in this work. This work was conducted to provide fundamental information from the study of equilibrium adsorption isotherms and to investigate the adsorption mechanisms in the adsorption of MB, Cu2+, and Cd2+ onto raw date pits. The fit of two models, namely Langmuir and Freundlich models, to experimental data obtained from the adsorption isotherms was checked. The adsorption capacities of the raw date pits towards MB and both Cu2+ and Cd2+ ions obtained from Langmuir and Freundlich models were found to be 277.8, 35.9, and 39.5 mg g(-1), respectively. Surface functional groups on the raw date pits surface substantially influence the adsorption characteristics of MB, Cu2+, and Cd2+ onto the raw date pits. The Fourier transform infrared spectroscopy (FTIR) studies show clear differences in both absorbances and shapes of the bands and in their locations before and after solute adsorption. Two mechanisms were observed for MB adsorption, hydrogen bonding and electrostatic attraction, while other mechanisms were observed for Cu2+ and Cd2+. For Cu2+, binding two cellulose/lignin units together is the predominant mechanism. For Cd2+. the predominant mechanism is by binding itself using two hydroxyl groups in the cellulose/lignin unit. (C) 2009 Elsevier B.V. All rights reserved.

An in vitro Study to Assess the Potential of a Unique Micro porous Algal Derived Cap Bone Void Filler in Comparison with Clinically-Used Bone Void Fillers

Macroporosity(>100µm) in bone void fillers is a known prerequisite for tissue regeneration, but recent literature has highlighted the added benefit of microporosity(0.5 - 10µm). The aim of this study was to compare the in vitro performances of a novel interconnective microporous hydroxyapatite (HA) derived from red algae to four clinically available macroporous calcium phosphate (CaP) bone void fillers. The use of algae as a starting material for this novel void filler overcomes the issue of sustainability, which overshadows continued use of scleractinian coral in the production of some commercially available materials, namely Pro-OsteonTM and Bio-Coral®. This study investigated the physicochemical properties of each bone voidfiller material using x-ray diffraction, fourier transform infrared spectroscopy, inductive coupled plasma, and nitrogen gas absorption and mercury porosimetry. Biochemical analysis, XTT, picogreen and alkaline phosphatase assays were used to evaluate the biological performances of the five materials. Results showed that algal HA is non-toxic to human foetal osteoblast (hFOB) cells and supports cell proliferation and differentiation. The preliminary in vitro testing of microporous algal-HA suggests that it is comparable to the four clinically approved macroporous bone void fillers tested. The results demonstrate that microporous algal HA has good potential for use in vivo and in new tissue engineered strategies for hard tissue repair.

Identification of a suitable sterilisation method for collagen derived from a marine Demosponge

Collagen is widely used as a biomedical material, and its importance is likely to grow as research and understanding progresses in this field. As a biomedical material, ensuring the sterility of collagen before use as, or incorporation into, a medical device is paramount. However, common sterilisation techniques can induce changes in the physical structure and protein chemistry of collagen, potentially affecting the performance. In this preliminary study, the influence of autoclaving, gamma irradiation and ethylene oxide gas sterilisation on the denaturation temperature and helical content of the collagen was evaluated using differential scanning calorimetry and Fourier transform infrared spectroscopy. Early results indicate that all sterilisation techniques affect collagen properties but suggest that the least damaging of the techniques investigated was y irradiation.

Competitive adsorption of aqueous metal ions on an oxidized nanoporous activated carbon\

Competitive adsorption is the usual situation in real applications, and it is of critical importance in determining the overall performance of an adsorbent. In this study, the competitive adsorption characteristics of all the combinations of binary mixtures of aqueous metal ion species Ca2+(aq), Cd2+(aq), Pb2+(aq), and Hg2+(aq) on a functionalized activated carbon were investigated. The porous structure of the functionalized active carbon was characterized using N-2 (77 K) and CO2 (273 K) adsorption. The surface group characteristics were examined by temperature-programmed desorption, Fourier transform infrared spectroscopy, Raman spectroscopy, acid/base titrations, and measurement of the point of zero charge (pH(PZC)). The adsorption of aqueous metal ion species M2+(aq), on acidic oxygen functional group sites mainly involves an ion exchange mechanism. The ratios of protons displaced to the amount of M2+(aq) metal species adsorbed have a linear relationship for both single-ion and binary mixtures of these species. Hydrolysis of metal species in solution may affect the adsorption, and this is the case for adsorption of Hg2+(aq) and Pb2+(aq). Competitive adsorption decreases the amounts of individual metal ions adsorbed, but the maximum amounts adsorbed still follow the order Hg2+(aq) > Pb2+(aq) > Cd2+(aq) > Ca2+(aq) obtained for single metal ion adsorption. The adsorption isotherms for single metal ion species were used to develop a model for competitive adsorption in binary mixtures, involving exchange of ions in solution with surface proton sites and adsorbed metal ions, with the species having different accessibilities to the porous structure. The model was validated against the experimental data.

Plasma polymerization of 2-iodothiophene

Continuous wave rf plasma polymerization of 2-iodothiophene has been studied using X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES), and Fourier transform infrared spectroscopy (FTIR). The variation in plasma polymer stoichiometry and the extent of monomer fragmentation are found to be critically dependent upon the electrical discharge power.

On-line FTIR spectroscopic investigations of methanol oxidation in a direct methanol fuel cell

A real-time Fourier transform infrared spectroscopy (FTIRS) analysis of the products of methanol oxidation in a prototype direct-methanol fuel cell operating at high temperatures (150 to 185°C) is reported here. The methanol oxidation products on platinum black and platinum-ruthenium catalyst surfaces were determined as a function of the fuel cell operating temperature, current density, and methanol/water mole ratio. Neither formaldehyde nor formic acid was detected in anode exhaust gas at all cell operating conditions. The product distributions of methanol oxidation obtained by on-line FTIRS are consistent with our previous results obtained by on-line mass spectroscopy under similar conditions. With pure methanol in anode feed, methanaldimethylacetal was found to be the main product, methyl formate and CO were also found. However, when water was present in the anode feed, the main product was CO , and the formation of methanaldimethylacetal and methyl formate decreased significantly with increase of the water/methanol mole ratio. Increase of cell operating temperature enhanced the formation of CO and decreased the formation of methanaldimethylacetal and methyl formate. Pt/Ru catalyst is more active for methanol oxidation and has a higher selectivity toward CO formation than Pt-black. Nearly complete methanol oxidation, i.e., the product was almost exclusively CO , was achieved using a Pt/Ru catalyst and a water/methanol mole ratio of 2 or higher in the anode feed at a temperature of 185°C or above.

Milling plant and soil material in plastic tubes over-estimates carbon and under-estimates nitrogen concentrations

Milling of plant and soil material in plastic tubes, such as microcentrifuge tubes, over-estimates carbon (C) and under-estimates nitrogen (N) concentrations due to the introduction of polypropylene into milled samples, as identified using Fourier-transform infra-red spectroscopy.

This study compares C and N concentrations of roots and soil milled in microcentrifuge tubes versus stainless steel containers, demonstrating that a longer milling time, greater milling intensity, smaller sample size and inclusion of abrasive sample material all increase polypropylene contamination from plastic tubes leading to overestimation of C concentrations by up to 8 % (0.08 g g(-1)).

Erroneous estimations of C and N, and other analytes, must be assumed after milling in plastic tubes and milling methods should be adapted to minimise such error.

Using Flory-Huggins phase diagrams as a pre-formulation tool for the production of amorphous solid dispersions; a comparison between hot-melt extrusion and spray drying

Objectives: Amorphous drug forms provide a useful method of enhancing the dissolution performance of poorly water-soluble drugs; however, they are inherently unstable. In this article, we have used Flory–Huggins theory to predict drug solubility and miscibility in polymer candidates, and used this information to compare spray drying and melt extrusion as processes to manufacture solid dispersions.
Method:  Solid dispersions were characterised using a combination of thermal (thermogravimetric analysis and differential scanning calorimetry) and spectroscopic (Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction methods. 
Key Findings: Spray drying permitted generation of amorphous solid dispersions to be produced across a wider drug concentration than melt extrusion. Melt extrusion provided sufficient energy for more intimate mixing to be achieved between drug and polymer, which may improve physical stability. It was also confirmed that stronger drug–polymer interactions might be generated through melt extrusion. Remixing and dissolution of recrystallised felodipine into the polymeric matrices did occur during the modulated differential scanning calorimetry analysis, but the complementary information provided from FTIR confirms that all freshly prepared spray-dried samples were amorphous with the existence of amorphous drug domains within high drug-loaded samples. 
Conclusion: Using temperature–composition phase diagrams to probe the relevance of temperature and drug composition in specific polymer candidates facilitates polymer screening for the purpose of formulating solid dispersions.