Michél K. Nieuwoudt

Microfossils of Polynesian cultigens in lake sediment cores from Rano Kau, Easter Island

Previous wetland vegetation records from Easter Island showing deforestation and Polynesian agriculture are limited to cores that rely on pollen, with a single cultigen pollen type identified: Urticaceae/Moraceae, possibly Broussonetiapayrifera (paper mulberry). Here we redress this by also using phytolith and starch analyses on four lake sediment cores on a ~350-m transect along the southwest edge of Rano Kau, focusing on in-washed basal clayey layers. We also use a new method, Fourier transform infrared spectroscopy, to positively identify degraded starch collected from sedimentary deposits. The cores are the first samples recovered from an area in the lake that (a) lies below the relict village of Orongo, (b) is near a section of the crater believed to be most accessible from the Pacific coast, and (c) is far from the northern crater rim and receives high solar radiation, a likely benefit for crops of tropical origin. Pollen and phytoliths are abundant in the clayey layers and sparse in overlying layers of organic lake detritus and living rhizomes. Mixing of core deposits as a result of human activity has disordered the radiocarbon sequence, precluding development of an reliable chronology. Containing microfossils of several introduced cultigens, the clayey layers represent gardened terraces that have slumped into the lake. The data indicate large-scale deforestation and a mixed-crop production system including Broussonetiapapyrifera, Colocasiaesculenta (taro), Dioscoreaalata (greater yam), Ipomoeabatatas (sweet potato), Lagenariasiceraria (bottle gourd) and Musa (banana) sp. The data show (a) the potential for using the combined analyses to provide direct evidence of Polynesian horticulture on Easter Island and (b) that the island’s wetlands potentially hold extensive horticultural records. The study highlights the concept of ‘transported landscapes,’ whereby colonising people replace indigenous forests with artificial, imported agricultural landscapes.

Raman spectroscopy as an effective screening method for detecting adulteration of milk with small nitrogen-rich molecules and sucrose.

Adulteration of milk for commercial gain is acknowledged as a serious issue facing the dairy industry. Several analytical techniques can be used to detect adulteration but they often require time-consuming sample preparation, expensive laboratory equipment, and highly skilled personnel. Here we show that Raman spectroscopy provides a simple, selective, and sensitive method for screening milk, specifically for small nitrogen-rich compounds, such as melamine, urea, ammonium sulfate, dicyandiamide, and for sucrose. Univariate and multivariate statistical methods were used to determine limits of detection and quantification from Raman spectra of milk spiked with 50 to 1,000 mg/L of the N-rich compounds and 0.25 to 4% sucrose. Partial least squares (PLS) calibration provided limit of detection minimum thresholds <200mg/L (0.02%) for the 4 N-rich compounds and <0.8% for sucrose, without the need for surface-enhanced Raman spectroscopy. The results show high reproducibility (7% residual standard deviation) and 100% efficiency for screening of milk for these adulterants.

Short range order at the amorphous TiO2–water interface probed by silicic acid adsorption and interfacial oligomerization: An ATR-IR and 29Si MAS-NMR study

Adsorption and oligomerization of H(4)SiO(4) at the amorphous TiO(2)-aqueous interface were studied using in situ Attenuated Total Reflectance Infrared (ATR-IR) and ex situ solid state (29)Si nuclear magnetic resonance (NMR). The ATR-IR spectra indicate that a monomeric silicate species is present at low silicate surface concentration (Γ(Si)). Above a threshold Γ(Si) linear silicate oligomers are formed and these oligomers dominate the surface at high Γ(Si). Interestingly the ATR-IR spectra of H(4)SiO(4) on the TiO(2) surface are very similar to those previously observed on the poorly ordered iron oxide phase ferrihydrite. The (29)Si NMR spectrum of silicate on the TiO(2) surface shows the presence of Si in three states with chemical shifts corresponding to isolated monomers (Q(0)), the ends of linear oligomers (Q(1)) and the middle of linear oligomers (Q(2)). The ratio of the area of the Q(1) and Q(2) peaks was ≈2:1 which is consistent with the proposed formation of linear silicate trimers by insertion of a solution H(4)SiO(4) between adjacent suitably orientated adsorbed silicate monomers. A structural interpretation indicates that the observed interfacial silicate oligomerization behavior is a general phenomenon whereby bidentate silicate monomers on oxide surfaces are disposed towards forming linear oligomers by condensation reactions involving their two terminal Si-OH groups. The high surface curvature of nanometer sized spheres inhibits the formation of interfacial silicates with a higher degree of polymerization.

Influence of Heat Curing on Structure and Physicochemical Properties of Phenolic Acid Loaded Proteinaceous Electrospun Fibers

Effects of heat treatment on structure and physicochemical properties of zein (Ze) and gallic acid loaded zein (Ze-GA) electrospun fiber mats were investigated. The electrospun fiber mats displayed different surface and physicochemical properties after being heat-cured at 150 °C for 24 h, which were closely related to the initial amount of loaded gallic acid. The gallic acid was released from the Ze-GA fiber mats in a constant manner, but heat curing decreased the rate of release. Heat curing remarkably increased the molecular weight of the Ze and Ze-GA electrospun fiber mats. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) analysis of the fiber mats indicated variations in zein protein secondary structure after heat curing. (13)C solid state NMR (SS-NMR) confirmed the presence of a different chemical environment among the fiber mats. The fabrication of heat-cured zein based electrospun fibers in this study may find applications in the food packaging industry.

Rapid, sensitive, and reproducible screening of liquid milk for adulterants using a portable Raman spectrometer and a simple, optimized sample well

We have developed a powerful general spectroscopic method for rapidly screening liquid milk for adulterants by combining reflective focusing wells simply fabricated in aluminum with a small, portable Raman spectrometer with a focusing fiber optic probe. Hemispherical aluminum sample wells were specially designed to optimize internal reflection and sampling volume by matching the focal length of the mirror to the depth of focus of the laser probe. The technique was tested on milk adulterated with 4 different nitrogen-rich compounds (melamine, urea, dicyandiamide, and ammonium sulfate) and sucrose. No sample preparation of the milk was needed, and the total analysis time was 4min. Reliable sample presentation enabled average reproducibility of 8% residual standard deviation. The limit of detection interval measured from partial least squares calibrations ranged between 140 and 520mg/L for the 4 N-rich compounds and between 7,000 and 36,000mg/L (0.7-3.6%) for sucrose. The portability of the system and the reliability and reproducibility of this technique open opportunities for general, reagentless screening of milk for adulterants at the point of collection.

Screening for Adulterants in Liquid Milk Using a Portable Raman Miniature Spectrometer with Immersion Probe

A portable Raman system with an immersion fiber optic probe was assessed for point-of-collection screening for the presence of adulterants in liquid milk. N-rich adulterants and sucrose were measured in this proof-of-concept demonstration. Reproducibility, limit of detection range and other figures of merit such as specificity, sensitivity, ratio of predicted to standard deviation, standard error of prediction and root mean squared error for cross validation were determined from partial least squares (PLS) and partial least squares with discriminant analysis (PLS-DA) calibrations of milk mixtures containing 50–1000 ppm (parts per million) of melamine, ammonium sulphate, Dicyandiamide, urea and sucrose. The spectra were recorded by immersing the fiber optic probe directly in the milk solutions. Despite the high scattering background which was easily and reliably estimated and subtracted, the reproducibility for four N-rich compounds averaged to 11% residual standard deviation (RSD) and to 5% RSD for sucrose. PLS calibration models predicted the concentrations of separate validation sets with standard errors of prediction of between 44 and 76 ppm for the four N-rich compounds and 0.17% for sucrose. The sensitivity and specificity of the PLS-DA calibration were 92% and 89%, respectively. The study shows promise for use of portable mini Raman systems for routine rapid point-of-collection screening of liquid milk for the presence of adulterants, without the need for sample preparation or addition of chemicals.

Gold sputtered Blu-Ray disks as novel and cost effective sensors for surface enhanced Raman spectroscopy

Surface Enhanced Raman spectroscopy (SERS) offers sensitive and non-invasive detection of a variety of compounds as well as unparalleled information for establishing the molecular identity of both inorganic and organic compounds, not only in biological fluids but in all other aqueous and non-aqueous media. The localized hotspots produced through SERS at the solution/nanostructure interface of clustered gold or silver nano-particles enables detection levels of parts per trillion. Recent developments in advanced fabrication methods have enabled the manufacture of SERS substrates with repeatable surface nanostructures which provide reproducible quantitative analysis, historically a weakness of the SERS technique. In this paper we describe the novel use of gold sputtered Blu-Ray surfaces as SERS substrates. Blu-Ray disks provide ideal surfaces of SERS substrates with their repeatable and regular nano-gratings. We show that the unique surface features and composition of the recording surface enables the formation of gold nano-islands with nanogaps, simply through gold sputtering, and relate this to a 600 fold signal increase of the melamine Raman signal in aqueous solutions and detection to 68 ppb. Melamine is a triazine compound and appears not only as environmental contaminant in environmental groundwater but also as an adulterant in foods due to its high nitrogen content. We have shown significant SERS signal enhancements for spectra of melamine using gold-sputtered Blu-Ray disk surfaces, with reproducibility of 12%. Blu-Ray disks have a unique combination of design, surface features and composition of the recording surface which makes them ideal for preparation of SERS substrates by gold sputter-coating.

The antimicrobial action of polyaniline involves production of oxidative stress while functionalisation of polyaniline introduces additional mechanisms

Polyaniline (PANI) and functionalised polyanilines (fPANI) are novel antimicrobial agents whose mechanism of action was investigated. Escherichia coli single gene deletion mutants revealed that the antimicrobial mechanism of PANI likely involves production of hydrogen peroxide while homopolymer poly(3-aminobenzoic acid), P3ABA, used as an example of a fPANI, disrupts metabolic and respiratory machinery, by targeting ATP synthase and causes acid stress. PANI was more active against E. coli in aerobic, compared to anaerobic, conditions, while this was apparent for P3ABA only in rich media. Greater activity in aerobic conditions suggests involvement of reactive oxygen species. P3ABA treatment causes an increase in intracellular free iron, which is linked to perturbation of metabolic enzymes and could promote reactive oxygen species production. Addition of exogenous catalase protected E. coli from PANI antimicrobial action; however, this was not apparent for P3ABA treated cells. The results presented suggest that PANI induces production of hydrogen peroxide, which can promote formation of hydroxyl radicals causing biomolecule damage and potentially cell death. P3ABA is thought to act as an uncoupler by targeting ATP synthase resulting in a futile cycle, which precipitates dysregulation of iron homeostasis, oxidative stress, acid stress, and potentially the fatal loss of proton motive force.

Using near infrared spectroscopy to predict the lignin content and monosaccharide compositions of Pinus radiata wood cell walls

Near infrared (NIR) spectroscopy coupled with partial least squares (PLS-1) regression was used to predict the lignin contents and monosaccharide compositions of milled wood of Pinus radiata. The effects of particle size and moisture content were investigated by collecting NIR spectra of four sample types: large (<0.422mm) and small (<0.178mm) particles, in both ambient and dry conditions. PLS-1 models were constructed using mixtures of compression wood (CW) and opposite wood (OW) that provided a linear range of cell-wall compositions. Our results show that lignin contents and monosaccharide compositions of pure CWs and OWs can be successfully predicted using NIR spectra of all four sample types. However, large particles in ambient conditions have the most efficient preparation and the standard error (SE) values for lignin (2.10%), arabinose (0.34%), xylose (1.33%), galactose (2.54%), glucose (6.98%), mannose (1.48%), galacturonic acid (0.22%), glucuronic acid (0.06%), and 4-O-methylglucuronic acid (0.25%) were achieved.