Photon counting Raman spectroscopy: a benchmarking study vs surface plasmon enhancement.

We demonstrate a single-photon counting Raman spectroscope and benchmark it against conventional and surface-enhanced Raman spectroscopy. For direct comparison without ambiguity, we use the same solutions of Rhodamine 6G and a common optical setup with either a spectrometer or an acousto-optic tunable filter, whereas the surface enhancement is realized with immobilized Ag nanoparticles. Our results find that the single photon counting significantly elevates the detection sensitivity by up to eight orders of magnitude, arriving at a comparable level of surface-enhanced Raman spectroscopy. Another significant advantage is with the time-resolving measurement, where we demonstrate time-gated and time-correlated single-photon counting with sub-nanosecond resolution. It offers insights into the samples' transient responses and enables the isolation of Raman scattering from fluorescence signals.

Untargeted urine metabolite profiling by mass spectrometry aided by multivariate statistical analysis to predict prostate cancer treatment outcome.

Deciphering metabolomic networks has been demonstrated to provide valuable information for diagnosing and monitoring diseases. Herein, we report a technique to monitor untargeted urine metabolites to evaluate prostate cancer aggressiveness and treatment outcome. Direct chemical profiling of urine was achieved by a combined procedure of hyphenating laser diode thermal desorption with atmospheric pressure chemical ionization mass spectrometry (LDTD-APCI-MS). We describe a conceptually new approach to monitoring preoperative urinary metabolic alterations associated with prostate cancer recurrence. By evaluating mass/charge (m/z) ratios and peak intensities of ions detected by mass spectroscopy of urine samples, we revealed that intensities at m/z 313.2740 (±0.0003) and 341.3054 (±0.0006) attributable to monoacylglycerol backbone fragments from glycerides can be statistically correlated to disease progression.

Au-on-Ag nanostructure forin-situSERS monitoring of catalytic reactions.

Dual-functionality Au-on-Ag nanostructures (AOA) were fabricated on a silicon substrate by first immobilizing citrate-reduced Ag nanoparticles (Ag NPs, ∼43 nm in diameter), followed by depositing ∼7 nm Au nanofilms (Au NFs) via thermal evaporation. Au NFs were introduced for their catalytic activity in concave-convex nano-configuration. Ag NPs underneath were used for their significant enhancement factor (EF) in surface-enhanced Raman scattering (SERS)-based measurements of analytes of interest. Rhodamine 6G (R6G) was utilized as the Raman-probe to evaluate the SERS sensitivity of AOA. The SERS EF of AOA is ∼37 times than that of Au NPs. Using reduction of 4-nitrothiophenol (4-NTP) by sodium borohydride (NaBH4) as a model reaction, we demonstrated the robust catalytic activity of AOA as well as its capacity to continuously monitor via SERS the disappearance of reactant 4-NTP, emergence and disappearance of intermediate 4,4'-DMAB, and the appearance of product 4-ATP throughout the reduction process in real-time andin situ.

Fiber Coupled Near-Field Thermoplasmonic Emission from Gold Nanorods at 1100 K.

Nanostructured gold has attracted significant interest from materials science, chemistry, optics and photonics, and biology due to their extraordinary potential for manipulating visible and near-infrared light through the excitation of plasmon resonances. However, gold nanostructures are rarely measured experimentally in their plasmonic properties and hardly used for high-temperature applications because of the inherent instability in mass and shape due to the high surface energy at elevated temperatures. In this work, the first direct observation of thermally excited surface plasmons in gold nanorods at 1100 K is demonstrated. By coupling with an optical fiber in the near-field, the thermally excited surface plasmons from gold nanorods can be converted into the propagating modes in the optical fiber and experimentally characterized in a remote manner. This fiber-coupled technique can effectively characterize the near-field thermoplasmonic emission from gold nanorods. A direct simulation scheme is also developed to quantitively understand the thermal emission from the array of gold nanorods. The experimental work in conjunction with the direct simulation results paves the way of using gold nanostructures as high-temperature plasmonic nanomaterials, which has important implications in thermal energy conversion, thermal emission control, and chemical sensing.

Atomic, Molecular and Hybrid Oxygen Structures on Silver.

Interactions between oxygen and silver are important in many areas of science and technology, including materials science, medical, biomedical and environmental applications, spectroscopy, photonics, and physics. In the chemical industry, identification of oxygen structures on Ag catalysts is important in the development of environmentally friendly and sustainable technologies that utilize gas-phase oxygen as the oxidizing reagent without generating byproducts. Gas-phase oxygen adsorbs on Ag atomically by breaking the O-O bond and molecularly by preserving the O-O bond. Atomic O structures have Ag-O vibrations at 240-500 cm-1. Molecular O2 structures have O-O vibrations at significantly higher values of 870-1150 cm-1. In this work, we identify hybrid atomic-molecular oxygen structures, which form when one adsorbed O atom reacts with one lattice O atom on the surface or in the subsurface of Ag. Thus, these hybrid structures require dissociation of adsorbed molecular oxygen into O atoms but still possess the O-O bond. The hybrid structures have O-O vibrations at 600-810 cm-1, intermediate between the Ag-O vibrations of atomic oxygen and the O-O vibrations of molecular oxygen. The hybrid O-O structures do not form by a recombination of two adsorbed O atoms because one of the O atoms in the hybrid structure must be embedded into the Ag lattice. The hybrid oxygen structures are metastable and, therefore, serve as active species in selective oxidation reactions on Ag catalysts.

Nanostructured sapphire optical fiber embedded with Au nanorods for high-temperature plasmonics in harsh environments.

Sensors for harsh environments must exhibit robust sensing response and considerable thermal and chemical stability. We report the exploration of a novel all-alumina nanostructured sapphire optical fiber (NSOF) embedded with Au nanorods (Au NRs) for plasmonics-based sensing at high temperatures. Temperature dependence of the localized surface plasmon resonance (LSPR) of Au NRs was studied in conjunction with numerical calculations using the Drude model. It was found that LSPR of Au NRs changes markedly with temperature, red shifting and increasing in transmission amplitude as the temperature increases. Furthermore, this variation is highly localized through tunneling by overlapping the near-field of thin cladding and sapphire optical fiber. The NSOF embedded with Au NRs has the potential for sensing in advanced energy generation systems.

Plasmonic Au nanorods stabilized within anodic aluminum oxide pore channels against high-temperature treatment.

Au nanorods (Au NRs) are promising candidates for sensing applications due to their tunable localized surface plasmon resonance wavelength. At temperatures above 250 °C, however, these structures are morphologically unstable and tend to evaporate. We herein report a novel refractory plasmonic nanocomposite system comprising Au NRs entrapped in anodized aluminum oxide (AAO) scaffolds that are stable up to 800 °C. Au NRs were synthesized in the cylindrical pores of sapphire-supported AAO via in situ electroless deposition on catalytic Au nanoparticles (Au NPs) anchored on the pore walls. The morphological characteristics and surface-enhanced Raman scattering (SERS) functionality of Au NRs before and after heat treatment were evaluated using SEM, XRD and Raman spectroscopy. Compared to unconfined Au NRs that evolved into spherical particles at temperatures below 250 °C and subsequently evaporated from the substrate surface, the morphology of Au NRs in AAO was preserved upon heat treatment at temperatures up to 800 °C. Furthermore, by tuning the AAO scaffolds thickness and pore diameter, the aspect ratio (AR) of the entrapped Au NRs was varied from 2.4 to 7.8. The SERS sensitivity of Au NRs in AAO was found to increase with decreasing AR when the incident light was parallel to the rod longitudinal axis, in close agreement with the calculated fourth power of the local electromagnetic field using the finite-difference time domain method.

Thin-core fiber structures with overlays for sensing applications.

We investigate thin-core fiber-optic structures with film overlays that can be used for sensing applications. The structures are formed by a section of thin-core fibers (SM630 or SM450) spliced between standard SMF-28 fibers. The fibers are coated with overlays using the layer-by-layer assembly technology based on sequential alternating adsorption of polymer monolayers via electrostatic attraction. Transmission spectrum of the structures exhibits resonance dips caused by interaction between cladding modes. We measure the shifts of spectra with increasing thickness of the overlay and with pH value of the external medium. We calculate the shift of resonance wavelengths, which we compare with the experiment.

Strategy and method for nanoporous cladding formation on silica optical fiber.

We demonstrate the proof of an innovative concept of fabricating nanostructured aluminum oxide cladding on silica optical fiber. Our fabrication strategy entails freeze-coating aluminum on silica fiber and its subsequent anodization, resulting in the formation of anodized aluminum oxide (AAO) cladding with highly organized nanopore channels vertically aligned to the fiber axis. We show that the structure (diameter of pore channels and the porosity) of AAO cladding can be controlled by varying anodization conditions such as the type and concentration of electrolyte solutions and applied voltage. The versatility of AAO as a cladding with tunable structural and optical characteristics and/or a host of other functional nanostructures within the pore channels has the potential to enable a new class of specialty optical fiber for new sensor architecture and applications.

Lab-on-fiber optofluidic platform for in situ monitoring of drug release from therapeutic eluting polyelectrolyte multilayers.

A lab-on-fiber (LOF) optofluidic platform that provides physiologically relevant microenvironment was developed by integrating a long period grating (LPG) coupled with high order cladding mode to achieve high index sensitivity and a liquid-tight capillary tube assembly as a microfluidic chamber for LPG to mimic physiologically relevant microenvironment. We demonstrate the utility of LOF for in situ monitoring the construction of the [chitosan (CHI)/poly (acrylic acid) (PAA)/gentamicin sulfate (GS)/PAA]n multilayers at monolayer resolution as well as evaluating the rate of GS release at a flow rate of 0.127 mL/min at 37 °C in real time. We reveal that GS is released at a faster rate under the dynamic flow condition than in a static medium. Our findings underscore the importance of conducting drug release studies in physiologically relevant conditions.

Long-period gratings inscribed in photonic crystal fiber by symmetric CO(2) laser irradiation: erratum.

This erratum amends the wrongly cited NSF grant number in acknowledgment section in our publication.

Advantage of multi-mode sapphire optical fiber for evanescent-field SERS sensing.

An unclad, multi-mode single crystal sapphire fiber was used as a platform, and immobilized colloidal Ag nanoparticles (NPs) were used as enabler, for evanescent-field fiber-optic sensing via surface-enhanced Raman scattering (SERS) of Rhodamine 6G (R6G) solution. The dependence of the measured Raman intensity on NP coverage density (to a maximum of 120 particles/µm²) as well as the coverage length (to a maximum of 6 cm) was investigated. We demonstrate the utility of SERS-active sapphire fibers for sensitive measurements (10⁻8 M R6G). We further reveal, with the aid of theoretical analysis, that multi-mode fiber offers a significant advantage compared to its single-mode counterpart because the former allows two orders of magnitude higher particle coverage density than the latter to maximize SERS benefit, while maintaining the dominance of Raman gain despite the competitive interplay of NP-induced absorption and scattering loss along the interaction path length.

Long-period gratings inscribed in photonic crystal fiber by symmetric CO2 laser irradiation.

Long-period gratings (LPGs) inscribed in endlessly single mode (ESM) photonic crystal fibers (PCFs) with symmetric and asymmetric CO2 laser irradiation are investigated both numerically and experimentally. Parallel results from conventional single mode fibers (SMFs) are presented for comparison. Theoretical predictions, transmission measurements, and near-field imaging indicate that, regardless of the fiber type, symmetric index perturbation induced by laser irradiation with the aid of a 120° gold-coated reflecting mirror results in LP(0n) symmetric mode coupling, while asymmetric irradiation without using the mirror leads to LP(1n) asymmetric mode coupling. Our results show that, because of the azimuthally anisotropic hexagonal cladding structure, symmetric irradiation yields far more reproducible LPGs in PCFs than asymmetric irradiation. On the other hand, the irradiation symmetry has little effect on the reproducibility of LPGs inscribed in SMFs due to the isotropy of its all-solid cladding structure.

Long-period grating and its cascaded counterpart in photonic crystal fiber for gas phase measurement.

Regular and cascaded long period gratings (LPG, C-LPG) of periods ranging from 460 to 590 µm were inscribed in an endlessly single mode photonic crystal fiber (PCF) using CO(2) laser for sensing measurements of helium, argon and acetylene. High index sensitivities in excess of 1700 nm/RIU were achieved in both grating schemes with a period of 460 µm. The sharp interference fringes in the transmission spectrum of C-PCF-LPG afforded not only greatly enhanced sensing resolution, but also accuracy when the phase-shift of the fringe pattern is determined through spectral processing. Comparative numerical and experimental studies indicated LP(01) to LP(03) mode coupling as the principal coupling step for both PCF-LPG and C-PCF-LPG with emergence of multi-mode coupling at shorter grating periods or longer resonance wavelengths.

Numerical and experimental investigation of long-period gratings in photonic crystal fiber for refractive index sensing of gas media.

We have used the finite-difference frequency-domain (FDFD) method to simulate the core mode to cladding mode couplings in long-period gratings (LPGs) in photonic crystal fiber (PCF). Four sets of LPG-PCF have been fabricated with respective periodicities of 590, 540, 515, and 490 µm, resulting in corresponding resonance wavelengths (RWs) of 1241, 1399, 1494, and 1579 nm. We show both theoretically and experimentally that the longer the RW, the more sensitive the LPG-PCF is to the index change in Ar. We demonstrate a robust sensitivity of 517 nm per refractive index unit using the LPG-PCF at 1579 nm RW.

Photonic crystal fiber for layer-by-layer assembly and measurements of polyelectrolyte thin films.

The cladding air channels of an endlessly single-mode photonic crystal fiber (PCF) and the high-index sensitivity of its long-period gratings (LPG) inscribed by CO(2) laser have been exploited to deposit poly(vinyl pyrrolidone) (PVPON)/poly(methacrylic acid) (PMAA) polyelectrolyte thin films via layer-by-layer assembly (LbL) and to measure the deposition process. We show that LbL can be controllably carried out within the axially aligned air channels. PCF-LPG is highly sensitive to the LbL process as reflected by ~1.625 nm shift in the resonance wavelength per polyelectrolyte layer incorporated. PCF-LPG is also very robust for in situ monitoring of the release of PVPON from cross-linked polyelectrolytes, which results in the formation of pH-responsive PMAA hydrogel. PCF-LPG containing the hydrogel exhibits well-behaved response to changes in solution pH over 2 to 7.5. We demonstrate that PCF-LPG is 2 orders of magnitude more sensitive than its traditional all-solid counterpart through parallel investigation.

Differential SERS activity of gold and silver nanostructures enabled by adsorbed poly(vinylpyrrolidone).

We report that poly(vinylpyrrolidone) (PVP), a common stabilizer of colloidal dispersions of noble metal nanostructures, has a dramatic effect on their surface-enhanced Raman scattering (SERS) activity and enables highly selective SERS detection of analytes of various type and charge. Nanostructures studied include PVP-stabilized Au-Ag nanoshells synthesized by galvanic exchange reaction of citrate-reduced Ag nanoparticles (NPs), as well as solid citrate-reduced Ag and Au NPs, both before and after stabilization with PVP. All nanostructures were characterized in terms of their size, surface plasmon resonance wavelength, surface charge, and chemical composition. While the SERS activities of the parent citrate-reduced Ag and Au NPs are similar for rhodamine 6G (R6G) and 1,2-bis(4-pyridyl)ethylene (BPE) at various pH values, PVP-stabilized nanostructures demonstrate large differences in SERS enhancement factors (EFs) between these analytes depending on their chemical nature and protonation state. At pH values higher than BPE's pK(a2) of 5.65, where the analyte is largely unprotonated, the PVP-coated Au-Ag nanoshells showed a high SERS EF of >10(8). In contrast, SERS EFs were 10(3)- to 10(5)-fold lower for the protonated form of BPE at lower pH values, or for the usually highly SERS-active cationic R6G. The differential SERS activity of PVP-stabilized nanostructures is a result of discriminatory binding of analytes within-adsorbed PVP monolayer and a subsequent increase of analyte concentration at the nanostructure surface. Our experimental and theoretical quantum chemical calculations show that BPE binding with PVP-stabilized Au-Ag nanoshells is stronger when the analyte is in its unprotonated form as compared to its cationic, protonated form at a lower pH.

Effect of oxidation on surface-enhanced Raman scattering activity of silver nanoparticles: a quantitative correlation.

We quantitatively studied, using X-ray photoelectron spectroscopy (XPS), oxidation of substrate-immobilized silver nanoparticles (Ag NPs) in a wide range of conditions, including exposure to ambient air and controlled ozone environment under UV irradiation, and we correlated the degree of silver oxidation with surface-enhanced Raman scattering (SERS) enhancement factors (EFs). The SERS activity of pristine and oxidized Ag NPs was assessed by use of trans-1,2-bis(4-pyridyl)ethylene (BPE) and sodium thiocynate as model analytes at the excitation wavelength of 532 nm. Our study showed that the exposure of Ag NPs to parts per million (ppm) level concentrations of ozone led to the formation of Ag(2)O and orders of magnitude reduction in SERS EFs. Such an adverse effect was also notable upon exposure of Ag NPs under ambient conditions where ozone existed at parts per billion (ppb) level. The correlated XPS and SERS studies suggested that formation of just a submonolayer of Ag(2)O was sufficient to decrease markedly the SERS EF of Ag NPs. In addition, studies of changes in plasmon absorption bands pointed to the chemical enhancement as a major reason for deterioration of SERS signals when substrates were pre-exposed to ambient air, and to a combination of changes in chemical and electromagnetic enhancements in the case of substrate pre-exposure to elevated ozone concentrations. Finally, we also found UV irradiation and ozone had a synergistic effect on silver oxidation and thus a detrimental effect on SERS enhancement of Ag NPs and that such oxidation effects were analyte-dependent, as a result of inherent differences in chemical enhancements and molecular binding affinities for various analytes.

Therapeutic prognosis of prostate cancer using surface-enhanced Raman scattering of patient urine and multivariate statistical analysis.

Surface-enhanced Raman scattering (SERS) is highly sensitive and label-free analytical technique based on Raman spectroscopy aided by field-multiplying plasmonic nanostructures. We report the use of SERS measurements of patient urine in conjunction with biostatistical algorithms to assess the treatment response of prostate cancer (PCa) in 12 recurrent (Re) and 63 nonrecurrent (NRe) patient cohorts. Multiple Raman spectra are collected from each urine sample using monodisperse silver nanoparticles (AgNPs) for Raman signal enhancement. Genetic algorithms-partial least squares-linear discriminant analysis (GA-PLS-LDA) was employed to analyze the Raman spectra. Comprehensive GA-PLS-LDA analyses of these Raman spectral features (p = 3.50 × 10-16 ) yield an accuracy of 86.6%, sensitivity of 86.0%, and specificity 87.1% in differentiating the Re and NRe cohorts. Our study suggests that SERS combined with multivariate GA-PLS-LDA algorithm can potentially be used to detect and monitor the risk of PCa relapse and to aid with decision-making for optimal intermediate secondary therapy to recurred patients.

Core-cladding mode coupling and recoupling in photonic crystal fiber for enhanced overlap of evanescent field using long-period gratings.

Excitation of cladding modes has been achieved using long-period (LPGs) inscribed in an endlessly single-mode photonic crystal fiber (ESM PCF) by CO(2) laser irradiation. Core-cladding mode coupling and recoupling has resulted in marked improvement in the evanescent field overlap throughout the cladding air channels in the PCF-LPG, compared to the PCF alone. Our numerical simulation has shown that design optimization of the PCF-LPG configuration can lead to a field power overlap as high as 22% with a confinement loss of less than 1 dB/m in the cladding mode.