Characterization of Green Paints in Ming and Qianlong Dynasties' Lin'xi Pavilion by Complimentary Techniques.

During conservation of the painted ceiling decoration of Lin'xi Pavilion in the Forbidden City, two distinct paint campaigns were isolated as a unique case study into architectural paint materials during both the Ming and Qing dynasties. Paint samples and cross sections from both paint generations were analyzed with SEM-EDX, time of flight-secondary ion mass spectrometry (ToF-SIMS), XRD, FTIR, and Raman spectroscopies. Similar organic and inorganic materials characteristic of these time periods were identified. The pigments of interest found in both paint generations were botallackite and atacamite polymorphs. This suggests a shift from natural mineral sources to synthetic copper-based pigments for these larger architectural projects.

Improving Prediction of Peroxide Value of Edible Oils Using Regularized Regression Models.

We present four unique prediction techniques, combined with multiple data pre-processing methods, utilizing a wide range of both oil types and oil peroxide values (PV) as well as incorporating natural aging for peroxide creation. Samples were PV assayed using a standard starch titration method, AOCS Method Cd 8-53, and used as a verified reference method for PV determination. Near-infrared (NIR) spectra were collected from each sample in two unique optical pathlengths (OPLs), 2 and 24 mm, then fused into a third distinct set. All three sets were used in partial least squares (PLS) regression, ridge regression, LASSO regression, and elastic net regression model calculation. While no individual regression model was established as the best, global models for each regression type and pre-processing method show good agreement between all regression types when performed in their optimal scenarios. Furthermore, small spectral window size boxcar averaging shows prediction accuracy improvements for edible oil PVs. Best-performing models for each regression type are: PLS regression, 25 point boxcar window fused OPL spectral information RMSEP = 2.50; ridge regression, 5 point boxcar window, 24 mm OPL, RMSEP = 2.20; LASSO raw spectral information, 24 mm OPL, RMSEP = 1.80; and elastic net, 10 point boxcar window, 24 mm OPL, RMSEP = 1.91. The results show promising advancements in the development of a full global model for PV determination of edible oils.

Raman hyperspectral imaging with multivariate analysis for investigating enzyme immobilization.

Directed enzyme evolution has led to significant application of biocatalysis for improved chemical transformations throughout the scientific and industrial communities. Biocatalytic reactions utilizing evolved enzymes immobilized within microporous supports have realized unique advantages, including notably higher enzyme stability, higher enzyme load, enzyme reusability, and efficient product-enzyme separation. To date, limited analytical methodology is available to discern the spatial and chemical distribution of immobilized enzymes, in which techniques for surface visualization, enzyme stability, or activity are instead employed. New analytical tools to investigate enzyme immobilization are therefore needed. In this work, development, application, and evaluation of an analytical methodology to study enzyme immobilization is presented. Specifically, Raman hyperspectral imaging with principal component analysis, a multivariate method, is demonstrated for the first time to investigate evolved enzymes immobilized onto microporous supports for biocatalysis. Herein we demonstrate the ability to spatially and spectrally resolve evolved pantothenate kinase (PanK) immobilized onto two commercially-available, chemically-diverse porous resins. This analytical methodology is able to chemically distinguish evolved enzyme, resin, and chemical species pertinent to immobilization. As such, a new analytical approach to study immobilized biocatalysts is demonstrated, offering potential wide application for analysis of protein or biomolecule immobilization.

A novel multivariate curve resolution-alternating least squares (MCR-ALS) methodology for application in hyperspectral Raman imaging analysis.

Multivariate curve resolution-alternating least squares (MCR-ALS) applied to hyperspectral Raman imaging is extensively used to spatially and spectrally resolve the individual, pure chemical species within complex, heterogeneous samples. A critical aspect of performing MCR-ALS with hyperspectral Raman imaging is the selection of the number of chemical components within the experimental data. Several methods have previously been proposed to determine the number of chemical components, but it remains a challenging task that if done incorrectly, can lead to the loss of chemical information. In this work, we show that the choice of 'optimal' number of factors in the MCR-ALS model may vary depending on the relative contribution of the targeted species to the overall spectral intensity. In a data set consisting of 27 hyperspectral Raman images of TiO2 polymorphs, it was observed that the more dominant species were best resolved with a parsimonious model. However, species with intensities near the noise level often needed more factors to be resolved than was predicted by standard methods. Based on the observations in this data set, we propose a new method that employs approximate reference spectra for determining optimal model complexity for identifying minor constituents with MCR-ALS.

Assessing utility of handheld laser induced breakdown spectroscopy as a means of Dalbergia speciation.

Many species of Dalbergia are prized hardwoods, generally referred to as 'Rosewood,' and used in high-end products due to their distinctive hue and scent. Despite more than 58 species of Dalbergia being listed as endangered in Appendix 1 of The Convention on International Trade in Endangered Species of Fauna and Flora (CITES), the illegal logging and trade of this timber is ongoing. In this work, a handheld laser induced breakdown spectrometer (LIBS) was used to analyze seven Dalbergia species and two other exotic hardwood species to evaluate the ability of handheld LIBS for rapid classification of Dalbergia in the field. The KNN model of the classification presented 80% to 90% sensitivity for discriminating between Dalbergia species in the training set. PLS-DA models were based on a binary decision tree structure. Cumulatively, the PLS-DA decision tree model showed greater than 97% sensitivity and 99% selectivity for prediction of Dalbergia species included in the training set. The data presented in the following study are promising for the use of handheld LIBS devices and both KNN and PLS-DA models for applications in customs screenings at the port of entry of hard woods, among others.

Spatial and spectral resolution of carbonaceous material from hematite (α-Fe2O3) using multivariate curve resolution-alternating least squares (MCR-ALS) with Raman microspectroscopic mapping: implications for the search for life on Mars.

The search for evidence of extant or past life on Mars is a primary objective of both the upcoming Mars 2020 rover (NASA) and ExoMars 2020 rover (ESA/Roscosmos) missions. This search will involve the detection and identification of organic molecules and/or carbonaceous material within the Martian surface environment. For the first time on a mission to Mars, the scientific payload for each rover will include a Raman spectrometer, an instrument well-suited for this search. Hematite (α-Fe2O3) is a widespread mineral on the Martian surface. The 2LO Raman band of hematite and the Raman D-band of carbonaceous material show spectral overlap, leading to the potential misidentification of hematite as carbonaceous material. Here we report the ability to spatially and spectrally differentiate carbonaceous material from hematite using multivariate curve resolution-alternating least squares (MCR-ALS) applied to Raman microspectroscopic mapping under both 532 nm and 785 nm excitation. For this study, a sample comprised of hematite, carbonaceous material, and substrate-adhesive epoxy in spatially distinct domains was constructed. Principal component analysis (PCA) reveals that both 532 nm and 785 nm excitation produce representative three-phase systems of hematite, carbonaceous material, and substrate-adhesive epoxy in the analyzed sample. MCR-ALS with Raman microspectroscopic mapping using both 532 nm and 785 nm excitation was able to resolve hematite, carbonaceous material, and substrate-adhesive epoxy by generating spatially-resolved chemical maps and corresponding Raman spectra of these spatially distinct chemical species. Moreover, MCR-ALS applied to the combinatorial data sets of 532 nm and 785 nm excitation, which contain hematite and carbonaceous material within the same locations, was able to resolve hematite, carbonaceous material, and substrate-adhesive epoxy. Using multivariate analysis with Raman microspectroscopic mapping, 785 nm excitation more effectively resolved hematite, carbonaceous material, and substrate-adhesive epoxy as compared to 532 nm excitation. To our knowledge, this is the first report of multivariate analysis methods, namely MCR-ALS, with Raman microspectroscopic mapping being employed to differentiate carbonaceous material from hematite. We have therefore provided an analytical methodology useful for the search for extant or past life on the surface of Mars.

Electrografted diazonium salt layers for antifouling on the surface of surface plasmon resonance biosensors.

Electrografted diazonium salt layers on the surface of surface plasmon resonance (SPR) sensors present potential for a significant improvement in antifouling coatings. A pulsed potential deposition profile was used in order to circumvent mass-transport limitations for layer deposition rate. The influence of number of pulses with respect to antifouling efficacy was evaluated by nonspecific adsorption surface coverage of crude bovine serum proteins. Instead of using empirical and rough estimated values, the penetration depth and sensitivity of the SPR instrument were experimentally determined for the calculation of nonspecific adsorption surface coverage. This provides a method to better examine antifouling surface coatings and compare crossing different coatings and experimental systems. Direct comparison of antifouling performance of different diazonium salts was facilitated by a tripad SPR sensor design. The electrografted 4-phenylalanine diazonium chloride (4-APhe) layers with zwitterionic characteristic demonstrate ultralow fouling.

Sensing with prism-based near-infrared surface plasmon resonance spectroscopy on nanohole array platforms.

Nanohole arrays exhibit unique surface plasmon resonance (SPR) characteristics according to hole periodicity, diameter, and excitation wavelength (λ(SPR)). This contribution investigates the SPR characteristics and surface sensitivity of various nanohole arrays with the aim of tuning the parameters for optimal sensing capability. Both the Bragg surface plasmons (SPs) arising from diffraction by the periodic holes and the traditional propagating SPs are characterized with emphasis on sensing capability of the propagating SPs. Several trends in bulk sensitivity and penetration depth were established, and the surface sensitivity was calculated from bulk sensitivity and penetration depth of the SPs for different analyte thicknesses. Increased accuracy and precision in penetration depth values were achieved by incorporating adsorbate effects on substrate permittivity. The optimal nanohole array conditions for highest surface sensitivity were determined (820 nm periodicity, 0.27 diameter/periodicity, and λ(SPR) = 1550 nm), which demonstrated an increase in surface sensitivity for the 10 nm analyte over continuous gold films at their optimal λ(SPR) (1300 nm) and conventional visible λ(SPR) (700 nm).

Analyzing atomic force microscopy images of virus-like particles by expectation-maximization.

Analysis of virus-like particles (VLPs) is an essential task in optimizing their implementation as vaccine antigens for virus-initiated diseases. Interrogating VLP collections for elasticity by probing with a rigid atomic force microscopy (AFM) tip is a potential method for determining VLP morphological changes. During VLP morphological change, it is not expected that all VLPs would be in the same state. This leads to the open question of whether VLPs may change in a continuous or stepwise fashion. For continuous change, the statistical distribution of observed VLP properties would be expected as a single distribution, while stepwise change would lead to a multimodal distribution of properties. This study presents the application of a Gaussian mixture model (GMM), fit by the Expectation-Maximization (EM) algorithm, to identify different states of VLP morphological change observed by AFM imaging.

Adsorbate-metal bond effect on empirical determination of surface plasmon penetration depth.

The penetration depth of surface plasmons is commonly determined empirically from the observed response for adsorbate loading on gold surface plasmon resonance (SPR) substrates. However, changes in the SPR spectrum may originate from both changes in the effective refractive index near the metal surface and changes in the metal permittivity following covalent binding of the adsorbate layer. Herein, the significance of incorporating an additional adsorbate-metal bonding effect in the calculation is demonstrated in theory and in practice. The bonding effect is determined from the nonzero intercept of a SPR shift versus adsorbate thickness calibration and incorporated into the calculation of penetration depth at various excitation wavelengths. Determinations of plasmon penetration depth with and without the bonding response for alkanethiolate-gold are compared and are shown to be significantly different for a thiol monolayer adsorbate system. Additionally, plasmon penetration depth evaluated with bonding effect compensation shows greater consistency over different adsorbate thicknesses and better agreement with theory derived from Maxwell's equation, particularly for adsorbate thicknesses that are much smaller (<5%) than the plasmon penetration depth. The method is also extended to a more practically applicable polyelectrolyte multilayer adsorbate system.

Development and investigation of a dual-pad in-channel referencing surface plasmon resonance sensor.

Herein, we describe the construction of a novel dual-pad referencing surface plasmon resonance (SPR) sensor utilizing electrolytic grafting of diazonium salts to individually functionalize two gold pads positioned in a single fluidic channel. Using a dove prism, a simple single axis optical train may be employed without compromising the analytical performance. Once functionalized, one pad is used as the analytical sensing pad for detection of molecular interactions while the other serves as the reference pad, compensating for background refractive index fluctuations. The reference pad effectively compensates bulk refractive index changes and temperature variations as well as other nonspecific effects. The sensor was applied to calibration of a pH-responsive polymer layer in the presence of bulk refractive index and temperature variations. Monitoring selective attachment of a protein is also demonstrated. To our knowledge, this is the first implementation of in-channel referencing SPR sensor utilizing diazonium salt-based surface chemistry.

DC magnetron sputtered polyaniline-HCl thin films for chemical sensing applications.

Thin films of conducting polymers exhibit unique chemical and physical properties that render them integral parts in microelectronics, energy storage devices, and chemical sensors. Overall, polyaniline (PAni) doped in acidic media has shown metal-like electronic conductivity, though exact physical and chemical properties are dependent on the polymer structure and dopant type. Difficulties arising from poor processability render production of doped PAni thin films particularly challenging. In this contribution, DC magnetron sputtering, a physical vapor deposition technique, is applied to the preparation of conductive thin films of PAni doped with hydrochloric acid (PAni-HCl) in an effort to circumvent issues associated with conventional thin film preparation methods. Samples manufactured by the sputtering method are analyzed along with samples prepared by conventional drop-casting. Physical characterization (atomic force microscopy, AFM) confirm the presence of PAni-HCl and show that films exhibit a reduced roughness and potentially pinhole-free coverage of the substrate. Spectroscopic evidence (UV-vis, FT-IR, and X-ray photoelectron spectroscopy (XPS)) suggests that structural changes and loss of conductivity, not uncommon during PAni processing, does occur during the preparation process. Finally, the applicability of sputtered films to gas-phase sensing of NH(3) was investigated with surface plasmon resonance (SPR) spectroscopy and compared to previous contributions. In summary, sputtered PAni-HCl films exhibit quantifiable, reversible behavior upon exposure to NH(3) with a calculated LOD (by method) approaching 0.4 ppm NH(3) in dry air.

Coaxial fiber-optic chemical-sensing excitation-emission matrix fluorometer.

Great reductions in the overall size and complexity of high throughput multichannel UV-visible fluorometers were achieved by coupling a compact optical fiber array to compact dispersive transmission optics. The coaxial configuration centers on the insertion of a silica/silica optical fiber into the hollow region of a UV-fused silica capillary waveguide. The outer core delivers the maximum power of the narrow wavelength region of the excitation spectrum created by coupling a xenon arc discharge lamp to a compact spectrometer. The molecular fluorescence resulting from the interaction of light emitted at the distal end of the hollow waveguide and the sample matrix is received and transmitted to a CCD via a compact dispersive grating-prism (grism) optical assembly. A linear array of the coaxial optical fibers permits a full excitation-emission matrix spectrum of the analyte matrix to be projected onto the face of the CCD. The in situ identification and monitoring of polycyclic aromatic hydrocarbons was carried out for the initial application testing for this prototype.

Investigation of a fiber optic surface plasmon spectroscopy in conjunction with conductivity as an in situ method for simultaneously monitoring changes in dissolved organic carbon and salinity in coastal waters.

A combination surface plasmon resonance (SPR) and conductivity sensor array was developed and implemented to demonstrate the ability to differentiate among changes in dissolved organic carbon (DOC) and salinity in coastal water. The array is capable of achieving sufficient spatial and temporal data density to better understand the cycling and fate of terrestrial DOC in coastal areas. DOC is the second largest source of bioreactive carbon in the environment and plays a key role in mediating microbial activity and generation of atmospheric CO(2). In the coastal areas, the salinity is also an important property in many applications, such as leak detection for landfill liners, saltwater intrusion to drinking water, marine environment monitoring, and seasonal climate prediction. Conductivity sensors are the industry standard for determining salinity in ocean systems. However, both conductivity and refractive index sensors, such as SPR spectroscopy based sensors, respond to salinity and DOC levels. To demonstrate the capability of the SPR sensor and a conductivity sensor to collect complimentary data useful in discrimination of salinity and DOC in coastal zone water, conductivity, SPR, and temperature data were collected during passage from the Juan de Fuca ridge area returning to the University of Washington docks.

Comparison of Spectroscopic Techniques for Determining the Peroxide Value of 19 Classes of Naturally Aged, Plant-Based Edible Oils.

The peroxide value of edible oils is a measure of the degree of oxidation, which directly relates to the freshness of the oil sample. Several studies previously reported in the literature have paired various spectroscopic techniques with multivariate analyses to rapidly determine peroxide values using field portable and process instrumentation; those efforts presented "best-case scenarios" with oils from narrowly defined training and test sets. The purpose of this paper is to evaluate the use of near- and mid-infrared absorption and Raman scattering spectroscopies on oil samples from different oil classes, including seasonal and vendor variations, to determine which measurement technique or combination thereof is best for predicting peroxide values. Following peroxide value assays of each oil class using an established titration-based method, global and global-subset calibration models were constructed from spectroscopic data collected on the 19 oil classes used in this study. Spectra from each optical technique were used to create partial least squares regression calibration models to predict the peroxide value of unknown oil samples. A global peroxide value model based on near-infrared (8 mm optical path length) oil measurements produced the lowest RMSEP (4.9), followed by 24 mm optical path length near infrared (5.1), Raman (6.9) and 50 µm optical path length mid-infrared (7.3). However, it was determined that the Raman RMSEP resulted from chance correlations. Global peroxide value models based on low-level fusion of the NIR (8 and 24 mm optical path length) data and all infrared data produced the same RMSEP of 5.1. Global subset models, based on any of the spectroscopies and olive oil training sets from any class (pure, extra light, extra virgin), all failed to extrapolate to the non-olive oils. However, the near-infrared global subset model built on extra virgin olive oil could extrapolate to test samples from other olive oil classes. This work demonstrates the difficulty of developing a truly global method for determining peroxide value of oils.

Multi-Analytical Study of Copper-Based Historic Pigments and their Alteration Products.

Copper-containing materials such as verdigris are commonly found in historic and artistic works of art, often at advanced states of decay. Applied on paper as inks and watercolors, many of which needed a binder such as gum arabic, the intrinsic instability of this pigment was known since the medieval period. The decay of verdigris (a mixture of copper acetates) as a pigment, as watercolor, and as a dye, was studied using a combination of vibrational (Fourier transform infrared) and X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) instrumental techniques. Changes in the copper oxidative states and the formation of copper oxide were monitored during accelerated degradation as powdered solids and applied on mockup samples (with and without binder). Accelerated aging of both commercially available and synthesized verdigris pigments showed the presence of an intermediate species, Cu(CH3COO)2•3Cu(OH)2•2H2O, which points to the beginning of the decay processes, that culminates in the formation of Cu(II) oxide. However, the presence of gum arabic seems to delay deterioration, by temporarily reducing Cu(II) to Cu(I), even when the final product includes Cu(II). This novel application of XPS and supporting techniques has significant implications in art conservation, as the identified behavior helps explain the better preservation state of some works of art.

Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) with Raman Imaging Applied to Lunar Meteorites.

Lunar meteorites provide a more random sampling of the surface of the Moon than do the returned lunar samples, and they provide valuable information to help estimate the chemical composition of the lunar crust, the lunar mantle, and the bulk Moon. As of July 2014, ∼96 lunar meteorites had been documented and ten of these are unbrecciated mare basalts. Using Raman imaging with multivariate curve resolution-alternating least squares (MCR-ALS), we investigated portions of polished thin sections of paired, unbrecciated, mare-basalt lunar meteorites that had been collected from the LaPaz Icefield (LAP) of Antarctica-LAP 02205 and LAP 04841. Polarized light microscopy displays that both meteorites are heterogeneous and consist of polydispersed sized and shaped particles of varying chemical composition. For two distinct probed areas within each meteorite, the individual chemical species and associated chemical maps were elucidated using MCR-ALS applied to Raman hyperspectral images. For LAP 02205, spatially and spectrally resolved clinopyroxene, ilmenite, substrate-adhesive epoxy, and diamond polish were observed within the probed areas. Similarly, for LAP 04841, spatially resolved chemical images with corresponding resolved Raman spectra of clinopyroxene, troilite, a high-temperature polymorph of anorthite, substrate-adhesive epoxy, and diamond polish were generated. In both LAP 02205 and LAP 04841, substrate-adhesive epoxy and diamond polish were more readily observed within fractures/veinlet features. Spectrally diverse clinopyroxenes were resolved in LAP 04841. Factors that allow these resolved clinopyroxenes to be differentiated include crystal orientation, spatially distinct chemical zoning of pyroxene crystals, and/or chemical and molecular composition. The minerals identified using this analytical methodology-clinopyroxene, anorthite, ilmenite, and troilite-are consistent with the results of previous studies of the two meteorites using electron microprobe analysis. To our knowledge, this is the first report of MCR-ALS with Raman imaging used for the investigation of both lunar and other types of meteorites. We have demonstrated the use of multivariate analysis methods, namely MCR-ALS, with Raman imaging to investigate heterogeneous lunar meteorites. Our analytical methodology can be used to elucidate the chemical, molecular, and structural characteristics of phases in a host of complex, heterogeneous geological, geochemical, and extraterrestrial materials.

Improved sensitivity and stability of amperometric enzyme microbiosensors by covalent attachment to gold electrodes.

Covalent attachment of glucose oxidase to a pre-activated 16-mercaptohexadecanoic acid at a gold ultramicroelectrode surface improves sensitivity, stability, and reproducibility of enzyme-based amperometric microbiosensors. Self-assembled monolayers of the N-hydroxysuccinimide ester of 16-mercaptohexandecanoic acid (NHS-MHA) at gold electrodes enable spontaneous covalent linking of glucose oxidase to the gold surface of ultramicroelectrodes. By self-assembling NHS-MHA for 30 min, approximately 93% of the electrode surface is covered, thereby maximizing both the number of attachment sites for glucose oxidase, and sufficient diffusion of hydrogen peroxide to the gold electrode. The glucose oxidase reaction with NHS-MHA was optimized at pH of 6.5, and at a temperature of 43 degrees C, resulting in a surface concentration of 6.8+/-0.6 x 10(11) enzymemoleculescm(-2). Thus obtained amperometric microbiosensors were calibrated in the range of 1-10mM providing excellent correlation with the theoretical prediction of the microbiosensor response. The reported sensitivity of these microbiosensors documents an improvement by one order of magnitude compared to other approaches for covalent enzyme attachment. This is attributed to the NHS-MHA layer spacing the enzymatic recognition interface further from the electrode surface, thereby minimizing quenching of the enzyme activity.

Raman Microspectroscopic Mapping with Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) Applied to the High-Pressure Polymorph of Titanium Dioxide, TiO2-II.

The high-pressure, α-PbO2-structured polymorph of titanium dioxide (TiO2-II) was recently identified in micrometer-sized grains recovered from four Neoarchean spherule layers deposited between ∼2.65 and ∼2.54 billion years ago. Several lines of evidence support the interpretation that these layers represent distal impact ejecta layers. The presence of shock-induced TiO2-II provides physical evidence to further support an impact origin for these spherule layers. Detailed characterization of the distribution of TiO2-II in these grains may be useful for correlating the layers, estimating the paleodistances of the layers from their source craters, and providing insight into the formation of the TiO2-II. Here we report the investigation of TiO2-II-bearing grains from these four spherule layers using multivariate curve resolution-alternating least squares (MCR-ALS) applied to Raman microspectroscopic mapping. Raman spectra provide evidence of grains consisting primarily of rutile (TiO2) and TiO2-II, as shown by Raman bands at 174 cm-1 (TiO2-II), 426 cm-1 (TiO2-II), 443 cm-1 (rutile), and 610 cm-1 (rutile). Principal component analysis (PCA) yielded a predominantly three-phase system comprised of rutile, TiO2-II, and substrate-adhesive epoxy. Scanning electron microscopy (SEM) suggests heterogeneous grains containing polydispersed micrometer- and submicrometer-sized particles. Multivariate curve resolution-alternating least squares applied to the Raman microspectroscopic mapping yielded up to five distinct chemical components: three phases of TiO2 (rutile, TiO2-II, and anatase), quartz (SiO2), and substrate-adhesive epoxy. Spectral profiles and spatially resolved chemical maps of the pure chemical components were generated using MCR-ALS applied to the Raman microspectroscopic maps. The spatial resolution of the Raman microspectroscopic maps was enhanced in comparable, cost-effective analysis times by limiting spectral resolution and optimizing spectral acquisition parameters. Using the resolved spectra of TiO2-II generated from MCR-ALS analysis, a Raman spectrum for pure TiO2-II was estimated to further facilitate its identification.

Fiber-optic surface plasmon resonance sensors in the near-infrared spectral region.

The sensitivity of fiber-optic surface plasmon resonance (SPR) sensors was improved by a factor of at least thirteen for aqueous solutions by modifying the tip geometry to allow interrogation of the surface plasmon (SP) band in the near-infrared (NIR) region. This was achieved by tuning the angle at the distal end of the SPR sensor to a dual taper of 71 degrees and 19 degrees . Using a low numerical aperture (NA) fiber-optic sensor, NA = 0.12, is necessary to obtain a functional SPR sensor working in the NIR region. Theoretical simulations using the Maxwell equations demonstrated that even higher enhancement is theoretically possible while maintaining a narrow spectral feature upon the excitation of the SP bands on gold surfaces. The manufacture of the SPR sensors yields good agreement between theoretical simulations and experimental observations. To investigate the properties of these fiber-optic SPR-NIR sensors, sucrose solutions ranging from 0 to 15 x 10(-3) in mole fraction were utilized. The increased sensitivity of the fiber-optic SPR sensors, when used to monitor biomarkers, would yield lower detection limits. The smaller sensing area, compared to planar or other fiber-optic SPR sensors, combined with an improvement of the sensitivity, would yield a dramatic reduction of the absolute amount detected by biosensors.