Distinctive Adsorption Mechanism and Kinetics of Immunoglobulin G on a Nanoscale Polymer Surface.

Elucidation of protein adsorption beyond simple polymer surfaces to those presenting greater chemical complexity and nanoscopic features is critical to developing well-controlled nanobiomaterials and nanobiosensors. In this study, we repeatedly and faithfully track individual proteins on the same nanodomain areas of a block copolymer (BCP) surface and monitor the adsorption and assembly behavior of a model protein, immunoglobulin G (IgG), over time into a tight surface-packed structure. With discrete protein adsorption events unambiguously visualized at the biomolecular level, the detailed assembly and packing states of IgG on the BCP nanodomain surface are subsequently correlated to various regimes of IgG adsorption kinetic plots. Intriguing features, entirely different from those observed from macroscopic homopolymer templates, are identified from the IgG adsorption isotherms on the nanoscale, chemically varying BCP surface. They include the presence of two Langmuir-like adsorption segments and a nonmonotonic regime in the adsorption plot. Via correlation to time-corresponding topographic data, the unique isotherm features are explained with single biomolecule level details of the IgG adsorption pathway on the BCP. This work not only provides much needed, direct experimental evidence for time-resolved, single protein level, adsorption events on nanoscale polymer surfaces but also signifies mutual linking between specific topographic states of protein adsorption and assembly to particular segments of adsorption isotherms. From the fundamental research viewpoint, the correlative ability to examine the nanoscopic surface organizations of individual proteins and their local as well as global adsorption kinetic profiles will be highly valuable for accurately determining protein assembly mechanisms and interpreting protein adsorption kinetics on nanoscale surfaces. Application-wise, such knowledge will also be important for fundamentally guiding the design and development of biomaterials and biomedical devices that exploit nanoscale polymer architectures.

Fundamental Properties of One-Dimensional Zinc Oxide Nanomaterials and Implementations in Various Detection Modes of Enhanced Biosensing.

Recent bioapplications of one-dimensional (1D) zinc oxide (ZnO) nanomaterials, despite the short development period, have shown promising signs as new sensors and assay platforms offering exquisite biomolecular sensitivity and selectivity. The incorporation of 1D ZnO nanomaterials has proven beneficial to various modes of biodetection owing to their inherent properties. The more widely explored electrochemical and electrical approaches tend to capitalize on the reduced physical dimensionality, yielding a high surface-to-volume ratio, as well as on the electrical properties of ZnO. The newer development of the use of 1D ZnO nanomaterials in fluorescence-based biodetection exploits the innate optical property of their high anisotropy. This review considers stimulating research advances made to identify and understand fundamental properties of 1D ZnO nanomaterials, and examines various biosensing modes utilizing them, while focusing on the unique optical properties of individual and ensembles of 1D ZnO nanomaterials specifically pertaining to their bio-optical applications in simple and complex fluorescence assays.

Highly photoresponsive, ZnO nanorod-based photodetector for operation in the visible spectral range.

While significant advances have been made for gold nanoparticle (AuNP)-coupled zinc oxide (ZnO) as visibly blind, ultraviolet photodetection devices, very few ZnO nanomaterial systems have been developed specifically for use in the visible wavelength regime. Further efforts to develop ZnO-based visible photodetectors (PDs) are still highly warranted in order to better understand the precise effect of AuNP load, operation wavelength, and beam position on the device output. In this study, we demonstrate significantly enhanced, photoresponse behaviors of AuNP-coupled ZnO nanorod (NR) network devices in the visible wavelength range with their photoresponse capacity comparable to, if not far exceeding, most commercial PDs as well as recently reported, visible, AuNP-coupled ZnO detectors. In addition, the nature and degree of the photoresponsivity enhancement are systematically elucidated by investigating their light-triggered electrical signals under varying incident wavelengths, AuNP amounts, and illumination positions. We discuss a possible photoconduction mechanism of our AuNP-coupled ZnO NR PDs and the origins of the high photoresponsivity. Specifically related to the AuNP amount-dependent photoresponse behaviors, the nanoparticle density yielding photoresponse maxima is explained as the interplay between localized surface plasmon resonance, plasmonic heating, and scattering in our photothermoelectric effect-driven device. We show that the AuNP-coupled ZnO NR PDs can be constructed via a straightforward method without the need for ultrahigh vacuum, sputtering procedures, or photo/electron-beam lithographic tools. Hence, the approach demonstrated in this study may serve as a convenient and viable means to advance the current state of ZnO-based PDs for operation in the visible spectral range with greatly increased photoresponsivity.

Emerging Cytokine Biosensors with Optical Detection Modalities and Nanomaterial-Enabled Signal Enhancement.

Protein biomarkers, especially cytokines, play a pivotal role in the diagnosis and treatment of a wide spectrum of diseases. Therefore, a critical need for advanced cytokine sensors has been rapidly growing and will continue to expand to promote clinical testing, new biomarker development, and disease studies. In particular, sensors employing transduction principles of various optical modalities have emerged as the most common means of detection. In typical cytokine assays which are based on the binding affinities between the analytes of cytokines and their specific antibodies, optical schemes represent the most widely used mechanisms, with some serving as the gold standard against which all existing and new sensors are benchmarked. With recent advancements in nanoscience and nanotechnology, many of the recently emerging technologies for cytokine detection exploit various forms of nanomaterials for improved sensing capabilities. Nanomaterials have been demonstrated to exhibit exceptional optical properties unique to their reduced dimensionality. Novel sensing approaches based on the newly identified properties of nanomaterials have shown drastically improved performances in both the qualitative and quantitative analyses of cytokines. This article brings together the fundamentals in the literature that are central to different optical modalities developed for cytokine detection. Recent advancements in the applications of novel technologies are also discussed in terms of those that enable highly sensitive and multiplexed cytokine quantification spanning a wide dynamic range. For each highlighted optical technique, its current detection capabilities as well as associated challenges are discussed. Lastly, an outlook for nanomaterial-based cytokine sensors is provided from the perspective of optimizing the technologies for sensitivity and multiplexity as well as promoting widespread adaptations of the emerging optical techniques by lowering high thresholds currently present in the new approaches.

Low-Index ZnO Crystal Plane-Specific Binding Behavior of Whole Immunoglobulin G Proteins.

Crystallographic surface-resolved examination of protein-ZnO interactions can greatly enhance the fundamental understanding of protein adsorption on these technologically important solid surfaces which, in turn, will be tremendously valuable for the emerging applications of ZnO-based biomaterials and biosensors. We examine experimentally and via computer simulations the intriguing differences in the adsorption preferences and binding behavior of whole immunoglobulin G (IgG) proteins to various, low-index ZnO crystal surfaces at the individual biomolecule level. By performing direct atomic force microscopy imaging, we determine that IgG predominantly binds to the ZnO plane of (101̅0) relative to the other three low-index planes of (0001), (0001̅), and (112̅0). This phenomenon is highly unusual, particularly considering the fact that the average binding energy of amino acids (AAs) on the ZnO (0001) facet is higher than that on the (101̅0) plane. In conjunction with combined Monte Carlo-molecular dynamics simulations, we further explain the possible origins of our unusual experimental findings with critical factors such as the specific spatial locations of strongly binding AAs in the protein and their spatial distributions on the exterior surface of the protein.

Fundamentals of nanoscale polymer-protein interactions and potential contributions to solid-state nanobioarrays.

Protein adsorption onto polymer surfaces is a very complex, ubiquitous, and integrated process, impacting essential areas of food processing and packaging, health devices, diagnostic tools, and medical products. The nature of protein-surface interactions is becoming much more complicated with continuous efforts toward miniaturization, especially for the development of highly compact protein detection and diagnostic devices. A large body of literature reports on protein adsorption from the perspective of ensemble-averaged behavior on macroscopic, chemically homogeneous, polymeric surfaces. However, protein-surface interactions governing the nanoscale size regime may not be effectively inferred from their macroscopic and microscopic characteristics. Recently, research efforts have been made to produce periodically arranged, nanoscopic protein patterns on diblock copolymer surfaces solely through self-assembly. Intriguing protein adsorption phenomena are directly probed on the individual biomolecule level for a fundamental understanding of protein adsorption on nanoscale surfaces exhibiting varying degrees of chemical heterogeneity. Insight gained from protein assembly on diblock copolymers can be effectively used to control the surface density, conformation, orientation, and biofunctionality of prebound proteins in highly miniaturized applications, now approaching the nanoscale. This feature article will highlight recent experimental and theoretical advances made on these fronts while focusing on single-biomolecule-level investigations of protein adsorption behavior combined with surface chemical heterogeneity on the length scale commensurate with a single protein. This article will also address advantages and challenges of the self-assembly-driven patterning technology used to produce protein nanoarrays and its implications for ultrahigh density, functional, and quantifiable protein detection in a highly miniaturized format.

Zinc oxide nanomaterials for biomedical fluorescence detection.

One-dimensional zinc oxide nanomaterials have been recently developed into novel, extremely effective, optical signal-enhancing bioplatforms. Their usefulness has been demonstrated in various biomedical fluorescence assays. Fluorescence is extensively used in biology and medicine as a sensitive and noninvasive detection method for tracking and analyzing biological molecules. Achieving high sensitivity via improving signal-to-noise ratio is of paramount importance in fluorescence-based, trace-level detection. Recent advances in the development of optically superior one-dimensional materials have contributed to this important biomedical area of detection. This review article will discuss major research developments that have so far been made in this emerging and exciting topical field. The discussion will cover a broad range of subjects including synthesis of zinc oxide nanorods (ZnO NRs), various properties differentiating them as suitable optical biodetection platforms, their demonstrated applicability in DNA and protein detection, and the nanomaterial characteristics relevant for biomolecular fluorescence enhancement. This review will then summarize the current status of ZnO NR-based biodetection and further elaborate future utility of ZnO NR platforms for advanced biomedical assays, based on their proven advantages. Lastly, present challenges experienced in this topical area will be identified and focal subject areas for future research will be suggested as well.

Principles and Applications of ZnO Nanomaterials in Optical Biosensors and ZnO Nanomaterial-Enhanced Biodetection.

Significant research accomplishments have been made so far for the development and application of ZnO nanomaterials in enhanced optical biodetection. The unparalleled optical properties of ZnO nanomaterials and their reduced dimensionality have been successfully exploited to push the limits of conventional optical biosensors and optical biodetection platforms for a wide range of bioanalytes. ZnO nanomaterial-enabled advancements in optical biosensors have been demonstrated to improve key sensor performance characteristics such as the limit of detection and dynamic range. In addition, all nanomaterial forms of ZnO, ranging from 0-dimensional (0D) and 1D to 2D nanostructures, have been proven to be useful, ensuring their versatile fabrication into functional biosensors. The employment of ZnO as an essential biosensing element has been assessed not only for ensembles but also for individual nanomaterials, which is advantageous for the realization of high miniaturization and minimal invasiveness in biosensors and biodevices. Moreover, the nanomaterials' incorporations into biosensors have been shown to be useful and functional for a variety of optical detection modes, such as absorption, colorimetry, fluorescence, near-band-edge emission, deep-level emission, chemiluminescence, surface evanescent wave, whispering gallery mode, lossy-mode resonance, surface plasmon resonance, and surface-enhanced Raman scattering. The detection capabilities of these ZnO nanomaterial-based optical biosensors demonstrated so far are highly encouraging and, in some cases, permit quantitative analyses of ultra-trace level bioanalytes that cannot be measured by other means. Hence, steady research endeavors are expected in this burgeoning field, whose scientific and technological impacts will grow immensely in the future. This review provides a timely and much needed review of the research efforts made in the field of ZnO nanomaterial-based optical biosensors in a comprehensive and systematic manner. The topical discussions in this review are organized by the different modes of optical detection listed above and further grouped by the dimensionality of the ZnO nanostructures used in biosensors. Following an overview of a given optical detection mode, the unique properties of ZnO nanomaterials critical to enhanced biodetection are presented in detail. Subsequently, specific biosensing applications of ZnO nanomaterials are discussed for ~40 different bioanalytes, and the important roles that the ZnO nanomaterials play in bioanalyte detection are also identified.

Strain-Modulated and Nanorod-Waveguided Fluorescence in Single Zinc Oxide Nanorod-Based Immunodetection.

Mechanical strain has been shown to be a versatile and tunable means to control various properties of nanomaterials. In this work, we investigate how strain applied to individual ZnO nanorods (NRs) can affect the fluorescence signals originated from external sources of bioanalytes, which are subsequently coupled and guided onto the NRs. Specifically, we determine how factors such as the NR length and protein concentration can influence the strain-induced changes in the waveguided fluorescence intensity along the NRs. We employ a protein of tumor necrosis factor-α (TNF-α) and a fluorophore-labeled antibody in a model immunoassay reaction, after which Alexa488-TNF-α immunocomplex is formed on ZnO NRs. We elucidate the relationships between the types as well as amounts of strain on the NRs and the fluorescence intensity originated from the Alexa488-TNF-α immunocomplexes. We show that tensile (compressive) strain applied to the NR leads to an increase (decrease) in the waveguided fluorescence signals. By assessing important optical phenomena such as fluorescence intensification on nanorod ends (FINE) and degree of FINE (DoF), we confirm their linear dependence with both the types and amounts of strain. Furthermore, the strain-induced changes in both FINE and DoF are found to be independent of protein concentration. We determine that NR length plays a critical role in obtaining high strain-dependence of the measured fluorescence signals. Particularly, we ascertain that longer NRs yield larger changes in both FINE and DoF in response to the applied strain, relative to shorter ones. In addition, longer NRs permit higher linear correlation between the protein concentration and the waveguided fluorescence intensity. These outcomes provide valuable insight into exploiting strain to enhance the detection of optical signals from bioanalytes, thus enabling their quantifications even at ultra-trace levels. Coupled with the use of individual ZnO NRs demonstrated in our measurements, this work may contribute to the development of a miniaturized, highly sensitive biosensor whose signal transduction is best optimized by the application of strain.

Self-Assembled Block Copolymers as a Facile Pathway to Create Functional Nanobiosensor and Nanobiomaterial Surfaces.

Block copolymer (BCP) surfaces permit an exquisite level of nanoscale control in biomolecular assemblies solely based on self-assembly. Owing to this, BCP-based biomolecular assembly represents a much-needed, new paradigm for creating nanobiosensors and nanobiomaterials without the need for costly and time-consuming fabrication steps. Research endeavors in the BCP nanobiotechnology field have led to stimulating results that can promote our current understanding of biomolecular interactions at a solid interface to the never-explored size regimes comparable to individual biomolecules. Encouraging research outcomes have also been reported for the stability and activity of biomolecules bound on BCP thin film surfaces. A wide range of single and multicomponent biomolecules and BCP systems has been assessed to substantiate the potential utility in practical applications as next-generation nanobiosensors, nanobiodevices, and biomaterials. To this end, this Review highlights pioneering research efforts made in the BCP nanobiotechnology area. The discussions will be focused on those works particularly pertaining to nanoscale surface assembly of functional biomolecules, biomolecular interaction properties unique to nanoscale polymer interfaces, functionality of nanoscale surface-bound biomolecules, and specific examples in biosensing. Systems involving the incorporation of biomolecules as one of the blocks in BCPs, i.e., DNA-BCP hybrids, protein-BCP conjugates, and isolated BCP micelles of bioligand carriers used in drug delivery, are outside of the scope of this Review. Looking ahead, there awaits plenty of exciting research opportunities to advance the research field of BCP nanobiotechnology by capitalizing on the fundamental groundwork laid so far for the biomolecular interactions on BCP surfaces. In order to better guide the path forward, key fundamental questions yet to be addressed by the field are identified. In addition, future research directions of BCP nanobiotechnology are contemplated in the concluding section of this Review.

Nanoscale protein arrays of rich morphologies via self-assembly on chemically treated diblock copolymer surfaces.

Well-controlled assembly of proteins on supramolecular templates of block copolymers can be extremely useful for high-throughput biodetection. We report the adsorption and assembly characteristics of a model antibody protein to various polystyrene-block-poly(4-vinylpyridine) templates whose distinctive nanoscale structures are obtained through time-regulated exposure to chloroform vapor. The strong adsorption preference of the protein to the polystyrene segment in the diblock copolymer templates leads to an easily predictable, controllable, rich set of nanoscale protein morphologies through self-assembly. We also demonstrate that the chemical identities of various subareas within individual nanostructures can be readily elucidated by investigating the corresponding protein adsorption behavior on each chemically distinct area of the template. In our approach, a rich set of intricate nanoscale morphologies of protein arrays that cannot be easily attained through other means can be generated straightforwardly via self-assembly of proteins on chemically treated diblock copolymer surfaces, without the use of clean-room-based fabrication tools. Our approach provides much-needed flexibility and versatility for the use of block copolymer-based protein arrays in biodetection. The ease of fabrication in producing well-defined and self-assembled templates can contribute to a high degree of versatility and simplicity in acquiring an intricate nanoscale geometry and spatial distribution of proteins in arrays. These advantages can be extremely beneficial both for fundamental research and biomedical detection, especially in the areas of solid-state-based, high-throughput protein sensing.

Elucidation of novel nanostructures by time-lapse monitoring of polystyrene-block-polyvinylpyridine under chemical treatment.

Nanoscale micellar structures of polystyrene-block-polyvinylpyridine (PS-b-PVP) diblock copolymers have proven their effectiveness in lithography and biological detection by serving as a choice material to produce nanoscale guides and delivery systems in a straightforward and rapid manner through self-assembly. Such applications can greatly benefit from having high versatility for the selection of template sizes (pattern repeat spacing) and shapes (pattern geometry), especially when reaching a size regime that conventional top-down fabrication techniques may not readily be able to provide desired feature dimensions. Selective chemical treatments of the diblock copolymers are one of the useful methods yielding a rich set of nanoscale features on PS-b-PVP. Exposure to selective vapor can induce reorganization of the polymeric chains of PS-b-PVP and alter the original micellar nanostructures. In this Article, we identify for the first time a host of new nanostructures formed at different stages of chloroform vapor annealing by performing time-lapse atomic force microscopy measurements. We determine key, time-dependent, topological parameters defining each nanostructure and present the likely scenario of polymeric chain reorganization during the morphological evolution of the diblock polymer nanodomains over time. We also ascertain intermediate morphological states containing the characteristic nanostructures from two consecutive phases as well as transition states appearing for a short time in between two subsequent phases. These research efforts may not only provide insight into the domain evolution steps of the micellar to the cylindrical structures of PS-b-PVP but may also be technologically advantageous for subwavelength mask design in nanolithography and high-density array fabrication in high throughput biodetection.

Employing heavy metal-free colloidal quantum dots in solution-processed white light-emitting diodes.

We report in this communication the design and fabrication of solution-processed white light-emitting diodes (LEDs) containing a bilayer of heavy metal-free colloidal quantum dots (QDs) and polymer in the device active region. White electroluminescence was obtained in the LEDs by mixing the red emission of ZnCuInS/ZnS core/shell QDs and the blue-green emission of poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine). A high color rendering index of 92 was achieved as compared to a 5310 K blackbody reference by virtue of broadband emission of the QDs. The Commission Internationale de l'Eclairage chromaticity coordinates of the white LED output exhibit a distinctive bias dependence. Finally, aging of the white LEDs was studied, revealing the difference between the photochemical stabilities of the QDs and polymer molecules and the consequent effect on the color evolution of the LEDs.

Elucidation of Strain-Dependent, Zinc Oxide Nanorod Response for Nanorod-Guided Fluorescence Intensity.

In this work, we examine how strain exerted on individual ZnO nanorods (NRs) can influence the fluorescence signals that are emitted from fluorophore molecules and subsequently coupled into and guided along the NR. We elucidate the relationships between the incremental levels of compressive and tensile strain on the NRs and measured fluorescence intensity of a model fluorophore, rhodamine 6G (R6G), as a function of the position on the NRs. We reveal that compressive strain on the NRs leads to a decrease in the guided fluorescence signal, while tensile strain leads to an increase in the fluorescence intensity. Compared to an unstrained state, approximately 35% decrease (increase) in R6G fluorescence intensity was observed from ZnO NRs when they were under compressive strain of -14% (tensile strain of +10%). Further, our systematic acquisition of the incremental addition of uniaxial strain result in a linear relationship of the coupled fluorescence signal and the amount of applied strain. The degree of fluorescence intensification on nanorod ends (DoF), which is a quantitative indicator for the amount of R6G signals coupled into and waveguided to the NR ends compared to those on the main body, also exhibits a linear relationship with strain. These outcomes, in turn, demonstrate that strain alters the waveguiding capabilities of ZnO NRs in a predictable manner, which can be exploited to modulate and optimize fluorescence and other light signals emitted by a nearby source. Considering the wide utility of ZnO NRs in photonics, optoelectronics, and sensors, insights from our study may be highly valuable to effectively controlling and enhancing optical signals from chemical and biological analytes through strain.

Functional polymers in protein detection platforms: optical, electrochemical, electrical, mass-sensitive, and magnetic biosensors.

The rapidly growing field of proteomics and related applied sectors in the life sciences demands convenient methodologies for detecting and measuring the levels of specific proteins as well as for screening and analyzing for interacting protein systems. Materials utilized for such protein detection and measurement platforms should meet particular specifications which include ease-of-mass manufacture, biological stability, chemical functionality, cost effectiveness, and portability. Polymers can satisfy many of these requirements and are often considered as choice materials in various biological detection platforms. Therefore, tremendous research efforts have been made for developing new polymers both in macroscopic and nanoscopic length scales as well as applying existing polymeric materials for protein measurements. In this review article, both conventional and alternative techniques for protein detection are overviewed while focusing on the use of various polymeric materials in different protein sensing technologies. Among many available detection mechanisms, most common approaches such as optical, electrochemical, electrical, mass-sensitive, and magnetic methods are comprehensively discussed in this article. Desired properties of polymers exploited for each type of protein detection approach are summarized. Current challenges associated with the application of polymeric materials are examined in each protein detection category. Difficulties facing both quantitative and qualitative protein measurements are also identified. The latest efforts on the development and evaluation of nanoscale polymeric systems for improved protein detection are also discussed from the standpoint of quantitative and qualitative measurements. Finally, future research directions towards further advancements in the field are considered.

Protein-Polymer Interaction Characteristics Unique to Nanoscale Interfaces: A Perspective on Recent Insights.

Protein interactions at polymer interfaces represent a complex but ubiquitous phenomenon that demands an entirely different focus of investigation than what has been attempted before. With the advancement of nanoscience and nanotechnology, the nature of polymer materials interfacing proteins has evolved to exhibit greater chemical intricacy and smaller physical dimensions. Existing knowledge built from studying the interaction of macroscopic, chemically alike surfaces with an ensemble of protein molecules cannot be simply carried over to nanoscale protein-polymer interactions. In this Perspective, novel protein interaction phenomena driven by the presence of nanoscale polymer interfaces are discussed. Being able to discern discrete protein interaction events via simple visualization was crucial to attaining the much needed, direct experimental evidence of protein-polymer interactions at the single biomolecule level. Spatial and temporal tracking of particular proteins at specific polymer interfaces was made possible by resolving individual proteins simultaneously with those polymer nanodomains responsible for the protein interactions. Therefore, such single biomolecule level approaches taken to examine protein-polymer interaction mark a big departure from the mainstream approaches of collecting indirectly observed, ensemble-averaged protein signals on chemically simple substrates. Spearheading research efforts so far has led to inspiring initial discoveries of protein interaction mechanisms and kinetics that are entirely unique to nanoscale polymer systems. They include protein self-assembly/packing characteristics, protein-polymer interaction mechanisms/kinetics, and various protein functionalities on polymer nanoconstructs. The promising beginning and future of nanoscale protein-polymer research endeavors are presented in this article.

Low-threshold two-photon pumped ZnO nanowire lasers.

We report in this communication the two-photon absorption (TPA)-induced room-temperature lasing performance of ZnO nanowires. Under femtosecond pulse-excitation at lambda = 700 nm in the infrared regime, a remarkably low threshold of 160 microJ/cm(2) was observed for the TPA-induced lasing action, which is of the same order of magnitude as that measured for the linear lasing process. Time-resolved photoluminescence characterization of two-photon pumped ZnO nanowires reveals the presence of a fast decay (3-4 ps) in the stimulated emission as compared to the slow decay (50-70 ps) for the spontaneous emission. The TPA process in ZnO nanowires was characterized with the nonlinear transmission measurement, which uncovers an enhanced TPA coefficient, about 14.7 times larger than that of bulk ZnO samples. The observed TPA enhancement in ZnO nanowires accounts for the low threshold lasing behavior, and has been attributed to the intensified optical field confined within the nanowire waveguides.

Single nanomaterial level investigation of ZnO nanorod sulfidation reactions via position resolved confocal Raman spectroscopy.

Zinc oxide (ZnO) nanomaterials have been used as desulfurizing sorbents for gaseous streams, zinc sulfide (ZnS)-forming template lattices in nanomaterial synthesis, and agriculturally produced sulfur (S)-removing reagents from the environment. Although various nanoscale forms of ZnO have already been utilized widely for such purposes, there is currently a lack of fundamental insight into the sulfidation of ZnO nanomaterials at the single nanocrystal level. We demonstrate that position-resolved confocal Raman spectroscopy can be successfully used to reveal the sulfidation process of ZnO NRs occurring at the single nanomaterial level. We attained a single crystal level understanding of the facet-dependent sulfidation reactivity of ZnO NRs by tracking the same NRs with Raman spectroscopy before and after the sulfidation reaction and quantitatively analyzing various ZnS-induced phonon scattering intensities from different positions on the NRs. The trend in NR facet-dependent sulfidation reactivity is further substantiated by correlating it with the electron microscopy and fluorescence data measured from the same NRs. The insight obtained from this study may provide the much-needed fundamental knowledge base for designing optimal ZnO nanostructures beneficial to many technological and industrial applications exploiting the ZnO-to-ZnS conversion. Taken together with the well-established methods to synthesize ZnO nanomaterials of specific crystal shapes and structures, our findings from this study may be broadly applicable in formulating and optimizing more advanced, low-dimensional ZnO sorbents and scrubbers for highly effective S removal.

Position- and Polarization-Specific Waveguiding of Multi-Emissions in Single ZnO Nanorods.

We examine multiphoton-produced optical signals waveguided through single ZnO nanorods (NRs) using a newly developed, scanning offset-emission hyperspectral microscopy (SOHM) technique. Specifically, we concurrently analyze waveguiding behaviors of sum-frequency generation (SFG), deep-trap emissions (DTE), and coherent anti-Stokes Raman scattering (CARS) occurring in individual ZnO NRs. SOHM acquires spectrally-indexed and spatially-resolved intensity maps/spectra of waveguided light intensity while excitation/emission collection positions and light polarization are scanned. Hence, the powerful measurement capabilities of SOHM enable quantitative analyses of the different ZnO NR waveguiding behaviors specific to the multiphoton-generated emissions as a function of measurement position, light-matter interaction geometry, and the optical origin of the guided signal. We subsequently reveal the distinct waveguiding behaviors of single ZnO NRs pertaining to the SFG-, DTE-, and CARS-originated signals and discuss particularly attractive ZnO NR properties in CARS waveguiding.

Ultrasensitive detection of cytokines enabled by nanoscale ZnO arrays.

Early detection of disease markers can provide higher diagnostic power and improve disease prognosis. We demonstrate the use of zinc oxide nanorod (ZnO NR) arrays in a straightforward, reliable, and ultrasensitive detection of the cytokines interleukin-18 and tumor necrosis factor-alpha. Specifically, we exploit the fluorescence-enhancing properties of ZnO NR platforms in cytokine assays involving both a pure buffer and urine. The detection sensitivity achieved using this ZnO NR method is in the subfemtogram per milliliter level, which is 3-4 orders of magnitude more sensitive than conventional assay detection limits. This unparalleled detection sensitivity is achieved without the need for indirect enzyme reactions or specialized instrumentation. We highlight various advantages of using ZnO NR arrays in the ultrasensitive profiling of cytokine levels. Key advantages include robustness of NR arrays, simple and direct assay schemes, high-throughput and multiplexing capabilities, and the ability to correlate directly measured signals to cytokine levels. In conjunction with the extremely high sensitivity demonstrated in this work, our ZnO NR array-based approach may be highly beneficial in early detection of many cytokine-implicated diseases.