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      pH-Triggered Molecular Alignment for Reproducible SERS Detection via an AuNP/Nanocellulose Platform

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      Scientific Reports
      Nature Publishing Group

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          Abstract

          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 pK a. We developed an AuNP/bacterial cellulose (BC) nanocomposite platform and applied it to two common pollutants, carbamazepine (CBZ) and atrazine (ATZ) with pK a values of 2.3 and 1.7, respectively. Simple mixing of the analytes with AuNP/BC at pH < pK a 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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          Most cited references27

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          Determination of organic compounds in water using dispersive liquid-liquid microextraction.

          A new microextraction technique termed dispersive liquid-liquid microextraction (DLLME) was developed. DLLME is a very simple and rapid method for extraction and preconcentration of organic compounds from water samples. In this method, the appropriate mixture of extraction solvent (8.0 microL C2Cl4) and disperser solvent (1.00 mL acetone) are injected into the aqueous sample (5.00 mL) by syringe, rapidly. Therefore, cloudy solution is formed. In fact, it is consisted of fine particles of extraction solvent which is dispersed entirely into aqueous phase. After centrifuging, the fine particles of extraction solvent are sedimented in the bottom of the conical test tube (5.0 +/- 0.2 microL). The performance of DLLME is illustrated with the determination of polycyclic aromatic hydrocarbons (PAHs) in water samples by using gas chromatography-flame ionization detection (GC-FID). Some important parameters, such as kind of extraction and disperser solvent and volume of them, and extraction time were investigated. Under the optimum conditions the enrichment factor ranged from 603 to 1113 and the recovery ranged from 60.3 to 111.3%. The linear range was 0.02-200 microg/L (four orders of magnitude) and limit of detection was 0.007-0.030 microg/L for most of analytes. The relative standard deviations (RSDs) for 2 microg/L of PAHs in water by using internal standard were in the range 1.4-10.2% (n = 5). The recoveries of PAHs from surface water at spiking level of 5.0 microg/L were 82.0-111.0%. The ability of DLLME technique in the extraction of other organic compounds such as organochlorine pesticides, organophosphorus pesticides and substituted benzene compounds (benzene, toluene, ethyl benzene, and xylenes) from water samples were studied. The advantages of DLLME method are simplicity of operation, rapidity, low cost, high recovery, and enrichment factor.
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            Gold nanoparticle based label-free SERS probe for ultrasensitive and selective detection of trinitrotoluene.

            TNT is one of the most commonly used nitro aromatic explosives used for landmine and military purpose. Due to the significant detrimental effects, contamination of soil and groundwater with TNT is the major concern. Driven by the need to detect trace amounts of TNT from environmental samples, this article demonstrates for the first time a highly selective and ultra sensitive, cysteine modified gold nanoparticle based label-free surface enhanced Raman spectroscopy (SERS) probe, for TNT recognition in 2 pico molar (pM) level in aqueous solution. Due to the formation of Meisenheimer complex between TNT and cysteine, gold nanoparticles undergo aggregation in the presence of TNT via electrostatic interaction between Meisenheimer complex bound gold nanoparticle and cysteine modified gold nanoparticle. As a result, it formed several hot spots and provided a significant enhancement of the Raman signal intensity by 9 orders of magnitude through electromagnetic field enhancements. A detailed mechanism for termendous SERS intensity change has been discussed. Our experimental results show that TNT can be detected quickly and accurately without any dye tagging in lower pM level with excellent discrimination against other nitro compounds and heavy metals.
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              Occurrence and fate of carbamazepine, clofibric acid, diclofenac, ibuprofen, ketoprofen, and naproxen in surface waters.

              Although various single-concentration measurements of pharmaceuticals are available in the literature, detailed information on the variation over time of the concentration and the load in wastewater effluents and rivers and on the fate of these compounds in the aquatic environment are lacking. We measured the concentrations of six pharmaceuticals, carbamazepine, clofibric acid, diclofenac, ibuprofen, ketoprofen, and naproxen, in the effluents of three wastewater treatment plants (WWTPs), in two rivers and in the water column of Lake Greifensee (Switzerland) over a time period of three months. In WWTP effluents, the concentrations reached 0.95 microg/L for carbamazepine, 0.06 microg/L for clofibric acid, 0.99 microg/L for diclofenac, 1.3 microg/L for ibuprofen, 0.18 microg/L for ketoprofen, and 2.6 microg/L for naproxen. The relative importance in terms of loads was carbamazepine, followed by diclofenac, naproxen, ibuprofen, clofibric acid, and ketoprofen. An overall removal rate of all these pharmaceuticals was estimated in surface waters, under real-world conditions (in a lake), using field measurements and modeling. Carbamazepine and clofibric acid were fairly persistent. Phototransformation was identified as the main elimination process of diclofenac in the lake water during the study period. With a relatively high sorption coefficient to particles, ibuprofen might be eliminated by sedimentation. For ketoprofen and naproxen, biodegradation and phototransformation might be elimination processes. For the first time, quantitative data regarding removal rates were determined in surface waters under real-world conditions. All these findings are important data for a risk assessment of these compounds in surface waters.
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                Author and article information

                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group
                2045-2322
                11 December 2015
                2015
                : 5
                : 18131
                Affiliations
                [1 ]Department of Civil and Environmental Engineering, Virginia Tech , Blacksburg, Virginia
                [2 ]Virginia Tech Institute of Critical Technology and Applied Science (ICTAS) Sustainable Nanotechnology Center (VTSuN ), Blacksburg, Virginia
                [3 ]Center for the Environmental Implications of Nanotechnology (CEINT), Duke University , Durham, North Carolina
                Author notes
                Article
                srep18131
                10.1038/srep18131
                4676058
                26658696
                fe28aded-feb7-4bb3-aa6b-7eb46f58391e
                Copyright © 2015, Macmillan Publishers Limited

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 02 September 2015
                : 13 November 2015
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