Investigation of the effect of simulated lens yellowing, transparency loss and refractive error on in vivo resonance Raman spectroscopy

To separately investigate the impact of simulated age-related lens yellowing, transparency loss and refractive error on measurements of macular pigment (MP) using resonance Raman spectroscopy.

In vivo macular pigment measurements:a comparison of resonance Raman spectroscopy and heterochromatic flicker photometry

To investigate whether two methods of measuring macular pigment-namely, heterochromatic flicker photometry (HFP) and resonance Raman spectroscopy (RRS)--yield comparable data.

Engineering of Vis-NIR Metamaterials towards Revolutionary Ultrasensitive and Versatile Plasmonic Biosensors

By enabling subwavelength light localization and strong electromagnetic field enhancement, plasmonic biosensors have opened up a new realm of possibilities for a broad range of chemical and biological sensing applications owing to their label-free and real-time attributes. Although significant progress has been made, many fundamental and practical challenges still remain to be addressed. For instance, the plasmonic biosensors are nonselective sensing platforms; they are not well-suited to provide information regarding conformation or chemical fingerprint of unknown biomolecules. Furthermore, tunability of the plasmonic resonance in visible frequency regime is still limited; this will prevent their efficient and reproducible exploitation in single-molecule sensitivity. Here, we show that by engineering geometry of plasmonic metamaterials,1 consisting of periodic arrays of artificial split-ring resonators (SRRs), the plasmonic resonance of metamaterials could be tuned to visible-near infrared regimes (Vis-NIR) such that it allows parallel acquisition of optical transmission and highly surface-enhanced Raman (SERS) spectra from large functionalized SRR arrays. The Au SRRs were designed in form of alphabet letters (U, V, S, H, Y) with various line width (from 80 to 30 nm). By tailoring their size and shape, plasmonic resonance wavelength of the SRRs could be actively tuned so that it gives the strongest SERS effect under given excitation energy and polarization for biological and organic molecules. On the other hand, the plasmonic tunability was also achieved for a given SRR pattern by tuning the laser wavelength to obtain the highest electromagnetic field enhancement. The geometry- and laser-tunable channels typically provide an electromagnetic field enhancement as high as 20 times. This will provide the basis of versatile and multichannel devices for identification of different conformational states of Guanine-rich DNA, detection of a cancer biomarker nucleolin, and femtomolar sensitivity detection of food and drink additives. These results show that the tunable Vis-IR metamaterials are very versatile biosensing platforms and suggest considerable promise in genomic research, disease diagnosis, and food safety analysis.

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.

Sclera as a Surrogate Marker for Determining AGE-Modifications in Bruch's Membrane Using a Raman Spectroscopy-Based Index of Aging

PURPOSE. Raman spectroscopy is an effective probe of advanced glycation end products (AGEs) in Bruch's membrane. However, because it is the outermost layer of the retina, this extracellular matrix is difficult to analyze in vivo with current technology. The sclera shares many compositional characteristics with Bruch's membrane, but it is much easier to access for in vivo Raman analysis. This study investigated whether sclera could act as a surrogate tissue for Raman-based investigation of pathogenic AGEs in Bruch's membrane.

METHODS. Human sclera and Bruch's membrane were dissected from postmortem eyes (n = 67) across a wide age range (33-92 years) and were probed by Raman spectroscopy. The biochemical composition, AGEs, and their age-related trends were determined from data reduction of the Raman spectra and compared for the two tissues.

RESULTS. Raman microscopy demonstrated that Bruch's membrane and sclera are composed of a similar range of biomolecules but with distinct relative quantities, such as in the heme/collagen and the elastin/collagen ratios. Both tissues accumulated AGEs, and these correlated with chronological age (R(2) = 0.824 and R(2) = 0.717 for sclera and Bruch's membrane, respectively). The sclera accumulated AGE adducts at a lower rate than Bruch's membrane, and the models of overall age-related changes exhibited a lower rate (one-fourth that of Bruch's membrane) but a significant increase with age (P <0.05).

CONCLUSIONS. The results suggest that the sclera is a viable surrogate marker for estimating AGE accumulation in Bruch's membrane and for reliably predicting chronological age. These findings also suggest that sclera could be a useful target tissue for future patient-based, Raman spectroscopy studies. (Invest Ophthalmol Vis Sci 2011;52:1593-1598) DOI:10.1167/iovs.10-6554

Manipulating plasmon modes in tip-enhanced Raman microscopy

The influence of polarization on the plasmon modes excited in tip-enhanced near-field optical microscopy have been investigated using the Finite Difference Time Domain Method. Analysis of the calculated results have laid particular emphasis on the ability to align local field enhancements with the orientation of molecules in order to optimize Raman signals, with particular relevance to recent experimental work on carbon nanotubes.

The controlled fabrication and geometry tunable optics of gold nanotube arrays

Arrays of vertically aligned gold nanotubes are fabricated over several square centimetres which display a geometry tunable plasmonic extinction peak at visible wavelengths and at normal incidence. The fabrication method gives control over nanotube dimensions with inner core diameters of 15–30 nm, wall thicknesses of 5–15 nm and nanotube lengths of up to 300 nm. It is possible to tune the position of the extinction peak through the wavelength range 600–900 nm by varying the inner core diameter and wall thickness. The experimental data are in agreement with numerical modelling of the optical properties which further reveal highly localized and enhanced electric fields around the nanotubes. The tunable nature of the optical response exhibited by such structures could be important for various label-free sensing applications based on both refractive index sensing and surface-enhanced Raman scattering.

METAMATERIAL DEVICE AND USES THEREOF

The present invention relates to a logic gate, comprising a metamaterial surface enhanced Raman scattering (MetaSERS) sensor, comprising (a) alphabetical metamaterials in the form of split ring resonators operating in the wavelength range of from 560 to 2200 nm; and (b) a guanine (G) and thymine (T)-rich oligonucleotide that can, upon presence of potassium cations (K+), fold into a G-quadruplex structure, and in presence of Hg2+, form a T-Hg2+-T hairpin complex that inhibits or disrupts the G-quadruplex structure formed in presence of K+, as well as methods of operating and using such a logic gate.

Investigation of the chemical origin and evidential value of differences in the SERS spectra of blue gel inks

Highly swellable polymer films doped with Ag nanoparticle aggregates (poly-SERS films) have been used to record very high signal:noise ratio, reproducible surface-enhanced (resonance) Raman (SER(R)S) spectra of in situ dried ink lines and their constituent dyes using both 633 and 785 nm excitation. These allowed the chemical origins of differences in the SERRS spectra of different inks to be determined. Initial investigation of pure samples of the 10 most common blue dyes showed that the dyes which had very similar chemical structures such as Patent Blue V and Patent Blue VF (which differ only by a single OH group) gave SERRS spectra in which the only indications that the dye structure had been changed were small differences in peak positions or relative intensities of the bands. SERRS studies of 13 gel pen inks were consistent with this observation. In some cases inks from different types of pens could be distinguished even though they were dominated by a single dye such as Victoria Blue B (Zebra Surari) or Victoria Blue BO (Pilot Acroball) because their predominant dye did not appear in other inks. Conversely, identical spectra were also recorded from different types of pens (Pilot G7, Zebra Z-grip) because they all had the same dominant Brilliant Blue G dye. Finally, some of the inks contained mixtures of dyes which could be separated by TLC and removed from the plate before being analysed with the same poly-SERS films. For example, the Pentel EnerGel ink pen was found to give TLC spots corresponding to Erioglaucine and Brilliant Blue G. Overall, this study has shown that the spectral differences between different inks which are based on chemically similar, but nonetheless distinct dyes, are extremely small, so very close matches between SERRS spectra are required for confident identification. Poly-SERS substrates can routinely provide the very stringent reproducibility and sensitivity levels required. This, coupled with the awareness of the reasons underlying the observed differences between similarly coloured inks allows a more confident assessment of the evidential value of inks SERS and should underpin adoption of this approach as a routine method for the forensic examination of inks.

Development of sampling methods for Raman analysis of solid dosage forms of therapeutic and illicit drugs

The results of a study aimed at determining the most important experimental parameters for automated, quantitative analysis of solid dosage form pharmaceuticals (seized and model 'ecstasy' tablets) are reported. Data obtained with a macro-Raman spectrometer were complemented by micro-Raman measurements, which gave information on particle size and provided excellent data for developing statistical models of the sampling errors associated with collecting data as a series of grid points on the tablets' surface. Spectra recorded at single points on the surface of seized MDMA-caffeine-lactose tablets with a Raman microscope (lambda(ex) = 785 nm, 3 mum diameter spot) were typically dominated by one or other of the three components, consistent with Raman mapping data which showed the drug and caffeine microcrystals were ca 40 mum in diameter. Spectra collected with a microscope from eight points on a 200 mum grid were combined and in the resultant spectra the average value of the Raman band intensity ratio used to quantify the MDMA: caffeine ratio, mu(r), was 1.19 with an unacceptably high standard deviation, sigma(r), of 1.20. In contrast, with a conventional macro-Raman system (150 mum spot diameter), combined eight grid point data gave mu(r) = 1.47 with sigma(r) = 0.16. A simple statistical model which could be used to predict sigma(r) under the various conditions used was developed. The model showed that the decrease in sigma(r) on moving to a 150 mum spot was too large to be due entirely to the increased spot diameter but was consistent with the increased sampling volume that arose from a combination of the larger spot size and depth of focus in the macroscopic system. With the macro-Raman system, combining 64 grid points (0.5 mm spacing and 1-2 s accumulation per point) to give a single averaged spectrum for a tablet was found to be a practical balance between minimizing sampling errors and keeping overhead times at an acceptable level. The effectiveness of this sampling strategy was also tested by quantitative analysis of a set of model ecstasy tablets prepared from MDEA-sorbitol (0-30% by mass MDEA). A simple univariate calibration model of averaged 64 point data had R-2 = 0.998 and an r.m.s. standard error of prediction of 1.1% whereas data obtained by sampling just four points on the same tablet showed deviations from the calibration of up to 5%.