Browsing by Author "Wei, Haoran"

Now showing 1 - 7 of 7
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    Aerosol microdroplets exhibit a stable pH gradient
    Wei, Haoran; Vejerano, Eric P.; Leng, Weinan; Huang, Qishen; Willner, Marjorie R.; Marr, Linsey C.; Vikesland, Peter J. (2018-07-10)
    Suspended aqueous aerosol droplets (< 50 mu m) are microreactors for many important atmospheric reactions. In droplets and other aquatic environments, pH is arguably the key parameter dictating chemical and biological processes. The nature of the droplet air/water interface has the potential to significantly alter droplet pH relative to bulk water. Historically, it has been challenging to measure the pH of individual droplets because of their inaccessibility to conventional pH probes. In this study, we scanned droplets containing 4-mercaptobenzoic acid-functionalized gold nanoparticle pH nanoprobes by 2D and 3D laser confocal Raman microscopy. Using surface-enhanced Raman scattering, we acquired the pH distribution inside approximately 20-mu m-diameter phosphate-buffered aerosol droplets and found that the pH in the core of a droplet is higher than that of bulk solution by up to 3.6 pH units. This finding suggests the accumulation of protons at the air/water interface and is consistent with recent thermodynamic model results. The existence of this pH shift was corroborated by the observation that a catalytic reaction that occurs only under basic conditions (i.e., dimerization of 4-aminothiophenol to produce dimercaptoazobenzene) occurs within the high pH core of a droplet, but not in bulk solution. Our nanoparticle probe enables pH quantification through the cross-section of an aerosol droplet, revealing a spatial gradient that has implications for acid-base-catalyzed atmospheric chemistry.
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    Environmental science and engineering applications of nanocellulose-based nanocomposites
    Wei, Haoran; Rodriguez, Katia; Renneckar, Scott; Vikesland, Peter J. (The Royal Society of Chemistry, 2014-06-26)
    Compared with cellulose, the primary component of the paper we use every day, nanocellulose has a much smaller diameter (typically <10 nm) that renders it many unique properties. Amongst many others, these properties include high mechanical strength, large surface area and low visual light scattering. Nanocellulose can be obtained by disintegration of plant cellulose pulp or by the action of specific types of bacteria. Once produced, nanocellulose can be used to make transparent films, fibers, hydrogels, or aerogels that exhibit extraordinary mechanical, thermal, and optical properties. Each of these substrates is a suitable template or carrier for inorganic nanoparticles (NPs), thus enabling production of nanocomposites that possess properties of the two constituents. In this review, we focus on the preparation of nanocellulose, nanocellulose films, and nanocellulose papers, and introduce nanocellulose-based nanocomposites and their environmental applications.
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    Highly stable SERS pH nanoprobes produced by co-solvent controlled AuNP aggregation
    Wei, Haoran; Willner, Marjorie R.; Marr, Linsey C.; Vikesland, Peter J. (Royal Society of Chemistry, 2016-04-22)
    Production of gold nanoparticle (AuNP) surface-enhanced Raman spectroscopy (SERS) nanoprobes requires replicable aggregation to produce multimers with high signal intensity. Herein, we illustrate a novel, yet simple, approach to produce SERS nanoprobes through control of co-solvent composition. AuNP multimers were produced by mixing AuNP monomers in water : ethanol co-solvent for variable periods of time. By varying the water : ethanol ratio and the amount of 4-mercaptobenzoic acid (4-MBA) present, the aggregation rate can be systematically controlled. Thiolated poly(ethylene glycol) was then added to halt the aggregation process and provide steric stability. This approach was used to produce pH nanoprobes with excellent colloidal stability in high ionic strength environments and in complex samples. The pH probe exhibits broad pH sensitivity over the range 6–11 and we calculate that a single AuNP dimer in a 35 fL volume is sufficient to generate a detectable SERS signal. As a proof-of-concept, the probes were used to detect the intracellular pH of human prostate cancer cells (PC-3). The internalized probes exhibit a strong 4-MBA signal without any interfering bands from either the cells or the culture media and produce exceptionally detailed pH maps. pH maps obtained from 19 xy surface scans and 14 yz depth scans exhibit highly consistent intracellular pH in the range of 5 to 7, thus indicating the greater reliability and reproducibility of our pH probes compared with other probes previously reported in the literature. Our water : ethanol co-solvent production process is fast, simple, and efficient. Adjustment of solvent composition may become a powerful way to produce SERS tags or nanoprobes in the future.
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    pH-Triggered Molecular Alignment for Reproducible SERS Detection via an AuNP/Nanocellulose Platform
    Wei, Haoran; Vikesland, Peter J. (Nature, 2015-12-11)
    The low affinity of neutral and hydrophobic molecules towards noble metal surfaces hinders their detection by surface-enhanced Raman spectroscopy (SERS). Herein, we present a method to enhance gold nanoparticle (AuNP) surface affinity by lowering the suspension pH below the analyte pKa. We developed an AuNP/bacterial cellulose (BC) nanocomposite platform and applied it to two common pollutants, carbamazepine (CBZ) and atrazine (ATZ) with pKa values of 2.3 and 1.7, respectively. Simple mixing of the analytes with AuNP/BC at pH < pKa resulted in consistent electrostatic alignment of the CBZ and ATZ molecules across the nanocomposite and highly reproducible SERS spectra. Limits of detection of 3 nM and 11 nM for CBZ and ATZ, respectively, were attained. Tests with additional analytes (melamine, 2,4-dichloroaniline, 4-chloroaniline, 3-bromoaniline, and 3-nitroaniline) further illustrate that the AuNP/BC platform provides reproducible analyte detection and quantification while avoiding the uncontrolled aggregation and flocculation of AuNPs that often hinder low pH detection.
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    Plasmonic colorimetric and SERS sensors for environmental analysis
    Wei, Haoran; Hossein Abtahi, Seyyed M.; Vikesland, Peter J. (The Royal Society of Chemistry, 2015-03-10)
    The potential for water pollution outbreaks requires the development of rapid, yet simple detection methods for water quality monitoring. Plasmonic nanostructures such as gold (AuNPs) and silver (AgNPs) nanoparticles are compelling candidates for the development of highly sensitive biosensors due to their unique localized surface plasmon resonances (LSPRs). The LSPR of AuNPs and AgNPs lies in the visible and infrared light range and is sensitive to the composition, size, shape, surrounding medium, and aggregation state of these NPs. This plasmonic behavior provides the basis for fabrication of colorimetric sensors for environmental analyses. Furthermore, the LSPR also enhances the electromagnetic field near the NP surface, which provides the basis for surface-enhanced Raman spectroscopy (SERS) based detection. Organic or inorganic pollutants and pathogens can be detected and differentiated based upon the finger-print spectra that arise when they enter SERS-active hot spots. In this tutorial review, we summarize progress made towards environmental analysis based on LSPR-based colorimetric and SERS detection. The problems and challenges that have hindered the development of LSPR-based nanosensors for real-world environmental pollutant monitoring are extensively discussed.
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    Preparation and evaluation of nanocellulose-gold nanoparticle nanocomposites for SERS applications
    Wei, Haoran; Rodriguez, Katia; Renneckar, Scott; Leng, Weinan; Vikesland, Peter J. (The Royal Society of Chemistry, 2015-06-09)
    Nanocellulose is of research interest due to its extraordinary optical, thermal, and mechanical properties. The incorporation of guest nanoparticles into nanocellulose substrates enables production of novel nanocomposites with a broad range of applications. In this study, gold nanoparticle/bacterial cellulose (AuNP/BC) nanocomposites were prepared and evaluated for their applicability as surface-enhanced Raman scattering (SERS) substrates. The nanocomposites were prepared by citrate mediated in situ reduction of Au3+ in the presence of a BC hydrogel at 303 K. Both the size and morphology of the AuNPs were functions of the HAuCl4 and citrate concentrations. At high HAuCl4 concentrations, Au nanoplates form within the nanocomposites and are responsible for high SERS enhancements. At lower HAuCl4 concentrations, uniform nanospheres form and the SERS enhancement is dependent on the nanosphere size. The time-resolved increase in the SERS signal was probed as a function of drying time with SERS ‘hot-spots’ primarily forming in the final minutes of nanocomposite drying. The application of the AuNP/BC nanocomposites for detection of the SERS active dyes MGITC and R6G as well as the environmental contaminant atrazine is illustrated as is its use under low and high pH conditions. The results indicate the broad applicability of this nanocomposite for analyte detection.
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    Surface-Enhanced Raman Spectroscopy for Environmental Analysis: Optimization and Quantitation
    Wei, Haoran (Virginia Tech, 2018-02-27)
    Fast, sensitive, quantitative, and low-cost analysis of environmental pollutants is highly valuable for environmental monitoring. Due to its single-molecule sensitivity and fingerprint specificity, surface-enhanced Raman spectroscopy (SERS) has been widely employed for heavy metal, organic compound, and pathogen detection. However, SERS quantitation is challenging because 1) analytes do not stay in the strongest enhancing region ("hot spots") and 2) SERS reproducibility is poor. In this dissertation, gold nanoparticle/bacterial cellulose (AuNP/BC) substrates were developed to improve SERS sensitivity by increasing hot spot density within the laser excitation volume. Environmentally relevant organic amines were fixed at "hot spots" by lowering solution pH below the analyte pKa and thus enabling SERS quantitation. In addition, a new SERS internal standard was developed based upon the electromagnetic enhancement mechanism that relates Rayleigh (elastic) and Raman (in-elastic) scattering. Rayleigh scattering arising from the amplified spontaneous emission of the excitation laser was employed as a normalization factor to minimize the inherent SERS signal variation caused by the heterogeneous distribution of "hot spots" across a SERS substrate. This highly novel technique, hot spot-normalized SERS (HSNSERS), was subsequently applied to evaluate the efficiency of SERS substrates, provide in situ monitoring of ligand exchange kinetics on the AuNP surface, and to reveal the relationship between the pKa of aromatic amines and their affinity to citrate-coated AuNPs (cit-AuNPs). Finally, colloidally stable stable pH nanoprobes were synthesized using co-solvent mediated AuNP aggregation and subsequent coating of poly(ethylene) glycol (PEG). These nanoprobes were applied for pH detection in cancer cells and in phosphate buffered aerosol droplets. The latter experiments suggest that stable pH gradients exist in aerosol droplets.