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Here we report on microfossil analysis of human dental calculus from Lapita (3000–2600 yr BP) and post-Lapita (2300–2000 yr BP) burials from Vao and Uripiv, Vanuatu. Phytoliths of introducedMusaand indigenousHeliconiain the calculus suggest the use of these taxa as food wrappings. Phytoliths and most other material in the calculus, namely sponge spicules, calcium oxalate crystals, xylem and charcoal, are unequivocal identifications. Another type of material, comprising degraded objects with a general morphology suggesting starch grains, is uncertain, however, as the unequivocal starch indicator, the Maltese cross, was not observed. We used a new method for calculus analysis, Fourier Transform InfraRed spectroscopy (FTIR), comparing the suspected starch with modern reference starch of prehistoric Pacific crops. Although the ancient FTIR analysis was limited to a small number of suspected starch grains, the results provide another line of evidence for starch. The calculus data are consistent with previous microfossil studies of Lapita deposits at the sites, and demonstrate the efficacy of this technique in contributing to the definition of the history of plant use and diet of early Pacific Island populations. [ABSTRACT FROM AUTHOR]

In this study, we utilize nanosecond and femtosecond direct laser writing for the generation of hydrophobic and hydrophilic microfluidic valves on a centrifugal microfluidic disk made of polycarbonate, without the need for wet-chemistry. Application of a femtosecond (fs) laser at 800 nm resulted in an increased contact angle, from ∼80° to ∼160°, thereby inducing the formation of a hydrophobic surface. In contrast, employing a nanosecond (ns) laser at 248 nm led to the formation of superhydrophilic surfaces. Morphological studies identified the enhancement in the surface roughness for the hydrophobic surfaces and the creation of smooth patterns for the hydrophilic surfaces. Chemical modifications in the laser-ablated samples were confirmed via Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis. These spectroscopic examinations revealed an increase of hydrophilic chemical groups on both surfaces, with a more pronounced increase on the nanosecond laser-modified surface. Furthermore, these surfaces were used as a case study for centrifugal microfluidic valves. These modified surfaces demonstrated peculiar pressure responses. Specifically, the hydrophobic valves necessitated a 29% increase in pressure for droplet passage through a microchannel. On the other hand, the superhydrophilic valves exhibited enhanced wettability, decreasing the pressure requirement for fluid flow through the modified area by 39%. However, similarly to the hydrophobic valves, the fluid exiting the hydrophilic valve area required an increased pressure. Overall, our study shows the potential for tailoring valve functionality in microfluidic systems through precise surface modifications using laser technology., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Photoinduced enhanced Raman spectroscopy (PIERS) is a new surface enhanced Raman spectroscopy (SERS) modality with a 680% Raman signal enhancement of adsorbed analytes over that of SERS. Despite the explosion in recent demonstrations, the PIERS mechanism remains undetermined. Using X-ray and time-resolved optical spectroscopies, electron microscopy, cyclic voltammetry, and density functional theory simulations, we elucidate the atomic-scale mechanism behind PIERS. Stable PIERS substrates were fabricated using self-organized arrays of TiO 2 nanotubes with controlled oxygen vacancy doping and size-controlled silver nanoparticles. The key source of PIERS vs SERS enhancement is an increase in the Raman polarizability of the adsorbed analyte upon photoinduced charge transfer. A balance between improved crystallinity, which enhances charge transfer due to higher electron mobility but decreases light absorption, and increased oxygen vacancy defect concentration, which increases light absorption, is critical. This work enables the rational design of PIERS substrates for sensing.

Prostate cancer (PCa) is a significant healthcare problem worldwide. Current diagnosis and treatment methods are limited by a lack of precise in vivo tissue analysis methods. Real-time cancer identification and grading could dramatically improve current protocols. Here, we report the testing of a thin optical probe using Raman spectroscopy (RS) and classification methods to detect and grade PCa accurately in real-time. We present the first clinical trial on fresh ex vivo biopsy cores from an 84 patient cohort. Findings from 2395 spectra measured on 599 biopsy cores show high accuracy for diagnosing and grading PCa. We can detect clinically significant PCa from benign and clinically insignificant PCa with 90% sensitivity and 80.2% specificity. We also demonstrate the ability to differentiate cancer grades with 90% sensitivity and specificity ≥82.8%. This work demonstrates the utility of RS for real-time PCa detection and grading during routine transrectal biopsy appointments., (© 2023 The Authors. Journal of Biophotonics published by Wiley-VCH GmbH.)

Sustained release of lidocaine from poly ethylene-co-vinyl acetate (EVA) implants can significantly improve pain management outcomes; however, poor drug loading is a major limitation. Recently, myristic acid was found to improve drug loading in EVA by inhibiting the crystallization of lidocaine. Here, lidocaine's interaction with myristic acid was studied by differential scanning calorimetry. Spectra of lidocaine-myristic acid mixtures were analysed using two-dimensional correlation (2DCOS) maps. Furthermore, spectroscopic analysis of EVA matrices containing lidocaine, alone and in combination with myristic acid, was also performed and drug release was evaluated in vitro. A eutectic was obtained on combining lidocaine and myristic acid at the molar ratio of 1:1 due to loss of myristic acid's dimeric conformation resulting in hydrogen bonding of its COOH group with lidocaine's amide I moieties. In EVA, hydrogen bonding between adjacent lidocaine molecules caused crystallization above a threshold concentration and could be inhibited by incorporation of myristic acid by eutectic formation. By altering the molecular confirmation and solid state properties of lidocaine in EVA, myristic acid reduces lidocaine crystallization, increases drug loading and influences drug release kinetics. Exploiting these interactions and promoting further hydrogen bonding through the addition of specific excipients presents a viable strategy to enhance and stabilise drug loading in polymer matrices for various applications., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Objective: Stress can play a role in the onset and exacerbation of psoriasis. Psychological interventions to reduce stress have been shown to improve psychological and psoriasis-related outcomes. This pilot randomised study investigated the feasibility of a brief interaction with a Paro robot to reduce stress and improve skin parameters, after a stressor, in patients with psoriasis., Methods: Around 25 patients with psoriasis participated in a laboratory stress task, before being randomised to either interact with a Paro robot or sit quietly (control condition) for 30 min. Raman spectroscopy and trans-epidermal water loss were measured at baseline, after the stressor and after the intervention as indexes of acute skin changes. Psychological variables, including self-reported stress and affect, were also measured at the three time-points., Results: No statistically significant differences between the two conditions were found for any of the outcomes measured. However, effect sizes suggest significance could be possible with a larger sample size. Changes in the psychological and Raman spectroscopy outcomes across the experimental session were found, indicating the feasibility of the procedures., Conclusion: This pilot study showed that a brief interaction with a Paro robot was a feasible intervention for patients with psoriasis, but future trials should broaden the inclusion criteria to try to increase recruitment rates. Studying people who are highly stressed, depressed or who are stress-responders may increase the power of the intervention to show effects using a longer-term intervention., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Law, Jarrett, Nieuwoudt, Holtkamp, Giglio and Broadbent.)

Raman spectroscopy has long been suggested as a potentially fast and sensitive method to monitor phytoplankton abundance and composition in marine environments. However, the pitfalls of visible detection methods in pigment-rich biological material and the complexity of their spectra have hindered their application as reliable in situ detection methods. In this study we combine 1064 nm confocal Raman spectroscopy with multivariate statistical analysis techniques (principle component analysis and partial leas-squares discriminant analysis) to reliably measure differences in the cell viability of a diatom species ( Chaetoceros muelleri ) and two haptophyte species ( Diacronema lutheri and Tisochrysis lutea ) of phytoplankton. The low fluorescence background due to this combined approach of NIR Raman spectroscopy and multivariate data analysis allowed small changes in the overall spectral profiles to be reliably monitored, enabling the identification of the specific spectral features that could classify cells as viable or nonviable regardless of their species. The most significant differences upon cell death were shown by characteristic shifts in the carotenoid bands at 1527 and 1158 cm -1 . The contributions from other biomolecules were less pronounced but revealed changes that could be identified using this combination of techniques., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Mid-infrared spectroscopy has been developed as a reliable and rapid tool for routine analysis of fat, protein, lactose and other components in liquid milk. However, variations within and between FTIR instruments, even within the same milk testing laboratory, present a challenge to the accuracy of measurement of particularly minor components in the milk, such as individual fatty acids or proteins. In this study we have used Analysis of variance-Simultaneous Component Analysis (ASCA), to monitor the spectral variation between and within each of four different FOSS FTIR spectrometers over each week in an independent milk testing laboratory over 4 years, between August 2017 and March 2021 (223 weeks). On everyday of each week, spectra of the same pilot milk sample were recorded approximately every hour on each of the four instruments. Overall, variations between instruments had the largest effect on spectral variation over each week, making a significant contribution every week. Within each instrument, day-to-day variations over the week were also significant for all but two of the weeks measured, however it contributed less to the variance overall. At certain times other factors not explained by weekday variation or inter-instrument variation dominated the variance in the spectra. Examination of the scores and loadings of the weekly ASCA analysis allowed identification of changes in the spectral regions affected by drifts in each instrument over time. This was found to particularly affect some of the fatty acid predictions., Competing Interests: We note that authors MN, GS, and SH are employees of Fonterra Co-operative Group Ltd., which supported this work. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Nieuwoudt, Giglio, Marini, Scott and Holroyd.)

During the process of studying some morphological characters of fish found in the food of the Australasian gannet Morus serrator breeding at Horuhoru Rock and Mahuki islands in the Hauraki Gulf, New Zealand, one carangid specimen of fish species Trachurus declivis out of the 25 fish specimens examined revealed seven small plastic particles in its stomach of different colours: black, red, blue, green, and transparent. Fourier transform infrared (FTIR) spectroscopy was used to identify the compositions of the particles as low and high density polyethylene, poly (methyl methacrylate), polypropylene, and a copolymer of butadiene, acrylonitrile, and methacrylamide. The plastic particles comprised several different shapes and sizes, ranging between 4.5 and 10 mm, and are therefore categorized as micro-and mesoplastic fragments., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Bone strength in human cortical bone is determined by the composition and structure of both the mineral and collagen matrices and influenced by factors such as age, gender, health, lifestyle and genetic factors. Age-related changes in the bone matrix are known to result in loss of mechanical strength and increased fragility. In this study we show how Raman spectroscopy, with its exquisite sensitivity to the molecular structure of bone, reveals new insights into age- and sex-related differences. Raman analysis of 18 samples of cortical hip bone obtained from people aged between 47-82 years with osteoarthritis (OA) found subtle changes in the lipid and collagen secondary structure, and the carbonate (CO 3 2- ) and phosphate (PO 4 3- ) mineral ratios in the bone matrix. Significant differences were observed between older and younger bones, and between older female and older male bones; no significant differences were observed between younger male and female bones. Older female bones presented the lowest mineral to matrix ratios (MMR) and highest CO 3 2- /PO 4 3- ratios, and relative to lipid/collagen -CH 2 deformation modes at 1450 cm -1 they had lowest overall mineral content, higher collagen cross linking and lipid content but lower levels of α-helix collagen structures than older male and younger male and female bones. These observations provided further insight on bone composition changes observed in the bone volume fraction (BV/TV) for the older female bones from microCT measurements on the same samples, while tissue mineral density (TMD) measurements had shown no significant differences between the samples.

Correction for 'Unexpected arene ligand exchange results in the oxidation of an organoruthenium anticancer agent: the first X-ray structure of a protein-Ru(carbene) adduct' by Matthew P. Sullivan et al., Chem. Commun., 2018, 54, 6120-6123.

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., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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., Competing Interests: The authors declare there are no competing interests.

The first X-ray structures of adducts formed between a RuII(N-heterocyclic carbene)(η6-p-cymene) compound and a protein are reported. Coordination to the protein induced the cleavage of the cymene ligand and EPR spectroscopy demonstrated the oxidation of the Ru centre.

The dechlorination of chlorinated organic pollutants by zero valent iron (ZVI) is an important water treatment process with a complex dependence on many variables. This complexity means that there are reported inconsistencies in terms of dechlorination with ZVI and the effect of ZVI acid treatment, which are significant and are as yet unexplained. This study aims to decipher some of this complexity by combining Raman spectroscopy with gas chromatography-mass spectrometry (GC-MS) to investigate the influence of the mineralogy of the iron oxide phases on the surface of ZVI on the reductive dechlorination of pentachlorophenol (PCP). Two electrolytic iron samples (ZVI-T and ZVI-H) were found to have quite different PCP dechlorination reactivity in batch reactors under anoxic conditions. Raman analysis of the "as-received" ZVI-T indicated the iron was mainly covered with the ferrous oxide (FeO) wustite, which is non-conducting and led to a low rate of PCP dechlorination. In contrast, the dominant oxide on the "as-received" ZVI-H was magnetite which is conducting and, compared to ZVI-T, the ZVI-H rate of PCP dechlorination was four times faster. Treating the ZVI-H sample with 1 N H 2 SO 4 made small change to the composition of the oxide layers and also minute change to the rate of PCP dechlorination. However, treating the ZVI-T sample with H 2 SO 4 led to the loss of wustite so that magnetite became the dominant oxide and the rate of PCP dechlorination increased to that of the ZVI-H material. In conclusion, this study clearly shows that iron oxide mineralogy can be a contributing factor to apparent inconsistencies in the literature related to ZVI performance towards dechlorination and the effect of acid treatment on ZVI reactivity.

Tilted stems of softwoods form compression wood (CW) and opposite wood (OW) on their lower and upper sides, respectively. More is known about the most severe form of CW, severe CW (SCW), but mild CWs (MCWs) also occur widely. Two grades of MCWs, MCW1 and MCW2, as well as SCW and OW were identified in the stems of radiata pine (Pinus radiata) that had been slightly tilted. The four wood types were identified by the distribution of lignin in the tracheid walls determined by fluorescence microscopy. A solution of the fluorescent dye acridine orange (AO) (0.02% at pH 6 or 7) was shown to metachromatically stain the tracheid walls and can also be used to determine lignin distribution. The lignified walls fluoresced orange to yellow depending on the lignin concentration. Microscopically well-characterized discs (0.5 mm diameter) of the wood types were used to determine lignin concentrations and lignin monomer compositions using the acetyl bromide method and thioacidolysis, respectively. Lignin concentration and the proportion of p-hydroxyphenyl units (H-units) relative to guaiacyl (G-units) increased with CW severity, with <1% H-units in OW and up to 14% in SCW. Lignin H-units can be used as a marker for CW and CW severity. Similar discs were also examined by Raman and FTIR micro-spectroscopies coupled with principal component analysis (PCA) to determine if these techniques can be used to differentiate the four different wood types. Both techniques were able to do this, particularly Raman micro-spectroscopy., (Copyright © 2017 Elsevier Masson SAS. All rights reserved.)

The implausible combination of centrifugal disc microfluidics and un-covered channels provides a simple way in which Raman spectroscopy can be implemented in industrially-relevant lab-on-a disc technology. Here we demonstrate these advantages by detecting very low concentrations of melamine in liquid milk, without pre-processing, without surface enhancement of the Raman signal and with no evidence of spectral contamination from the polymeric chip itself. A limit of detection (LOD) of 203 ppm for melamine in milk was achieved from Raman spectra of milk after drying. The centrifugal disc rotation and microchannel geometry results in rapid and reliable filling of the channels and in meniscus shape control, enabling reproducible Raman detection with quantitative precision.

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.

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., (Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.)

Nanostructured gold substrates provide chemically stable, signal-enhancing substrates for the sensitive detection of a variety of compounds through surface-enhanced Raman spectroscopy (SERS). Recent developments in advanced fabrication methods have enabled the manufacture of SERS substrates with repeatable surface nanostructures that provide reproducible quantitative analysis, historically a weakness of the SERS technique. Here, we describe the novel use of gold-sputtered Blu-ray disc surfaces as SERS substrates. The unique surface features and composition of the Blu-ray disc recording surface lead to the formation of gold nano-islands and nanogaps following simple gold sputtering, without any background peaks from the substrate. The SERS performance of this substrate is strong and reproducible with an enhancement factor (EF) of 10(3) for melamine. A limit of detection (LOD) for this compound of 70 ppb and average reproducibility of ±12 % were achieved. Gold-sputtered Blu-ray discs thus offer an excellent alternative to more exotic gold SERS substrates prepared by advanced, time-consuming and expensive methods. Graphical abstract AFM 3D images of 1-μm(2) sections of uncoated and gold-sputtered recordable Blu-ray disc (BD-R) surfaces and the SERS signal obtained on the gold-sputtered surface for a 1000 ppm aqueous solution of melamine.

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., (Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.)

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.

Gallic acid was successfully incorporated into zein ultra-fine fibres at different loading amount (5%, 10% and 20%) in order to develop an encapsulating technology for functional ingredient delivery using electrospinning. The produced fibres exhibit diameters ranging from 327 to 387 nm. The physical and thermal properties of encapsulated gallic acid were determined by X-ray diffraction (XRD) and differential scanning calorimetry (DSC); and the interaction between gallic acid and zein was attested by attenuated total reflection-Fourier transform infrared (ATR-FTIR). Thermogravimetric analysis (TGA) demonstrated a different thermal stability of the fabricated complex before and after the gallic acid incorporation. Lastly, the 1,1'-diphenyl-2-picrylhydrazyl (DPPH) assay showed that the gallic acid had retained its antioxidant activity after incorporation in zein electrospun fibres. Overall, electrospinning technique had shown promising results as an efficient and effective method for the preparation of sub-micron structured encapsulated functional ingredient that may find uses in food industry., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2011 Elsevier Inc. All rights reserved.)