Gopala Krishna Darbha

Selective Detection of Mercury (II) Ion Using Nonlinear Optical Properties of Gold Nanoparticles

Contamination of the environment with heavy metal ions has been an important concern throughout the world for decades. Driven by the need to detect trace amounts of mercury in environmental samples, this article demonstrates for the first time that nonlinear optical (NLO) properties of MPA-HCys-PDCA-modified gold nanoparticles can be used for rapid, easy and reliable screening of Hg(II) ions in aqueous solution, with high sensitivity (5 ppb) and selectivity over competing analytes. The hyper Rayleigh scattering (HRS) intensity increases 10 times after the addition of 20 ppm Hg(2+) ions to modified gold nanoparticle solution. The mechanism for HRS intensity change has been discussed in detail using particle size-dependent NLO properties as well as a two-state model. Our results show that the HRS assay for monitoring Hg(II) ions using MPA-HCys-PDCA-modified gold nanoparticles has excellent selectivity over alkali, alkaline earth (Li(+), Na(+), K(+), Mg(2+), Ca(2+)), and transition heavy metal ions (Pb(2+), Pb(+), Mn(2+), Fe(2+), Cu(2+), Ni(2+), Zn(2+), Cd(2+)).

Gold Nanoparticle-Based Miniaturized Nanomaterial Surface Energy Transfer Probe for Rapid and Ultrasensitive Detection of Mercury in Soil, Water, and Fish

Contamination of the environment with mercury has been an important concern throughout the world for decades. Exposure to high Hg levels can be harmful to the brain, heart, kidneys, lungs, and immune system of humans of all ages. Driven by the need to detect trace amounts of mercury in environmental samples, here we present a miniaturized, inexpensive, and battery-operated ultrasensitive gold nanoparticle-based nanomaterial surface energy transfer probe for screening mercury levels in contaminated soil, water, and fish which has excellent sensitivity (2 ppt) and selectivity for Hg(II) over competing analytes, with the largest fluorescence enhancement to date for sensing Hg(II) in environmental samples (1100-fold). The sensitivity of our probe to detect mercury level in soil, water, and fish is about 2-3 orders of magnitude higher than the EPA standard limit. We demonstrate that our probe is suitable to screen the amount of mercury in different fish, shellfish, and water samples from various commercial sources.

Gold-Nanorod-Based Sensing of Sequence Specific HIV-1 Virus DNA by Using Hyper-Rayleigh Scattering Spectroscopy

Infectious diseases caused by the human immunodeficiency virus (HIV) remain the leading killers of human beings worldwide, and function to destabilize societies in Africa, Asia, and the Middle East. Driven by the need to detect the presence of HIV viral sequence, here we demonstrate that the second-order nonlinear optical (NLO) properties of gold nanorods can be used for screening HIV-1 viral DNA sequence without any modification, with good sensitivity (100 pico-molar) and selectivity (single base-pair mismatch). The hyper-Rayleigh scattering (HRS) intensity increases 45 times when a label-free 145-mer, ss-gag gene DNA, was hybridized with 100 pM target DNA. The mechanism of HRS intensity change has been discussed with experimental evidence for higher multipolar contribution to the NLO response of gold nanorods.

Gold-nanoparticle-based miniaturized laser-induced fluorescence probe for specific DNA hybridization detection: studies on size-dependent optical properties

A compact, highly specific, inexpensive and user friendly optical fibre laser-induced fluorescence (LIF) sensor based on fluorescence quenching by nanoparticles has been developed to detect single-strand (ss-) DNA hybridization at femtomolar level. The fluorescence of fluorophore-tagged ss-DNA increases by a factor of 80 when it binds to a complimentary DNA, while the addition of single-base mismatch DNA had no effect on the fluorescence efficiency. We present theoretical and experimental results on dye fluorescence quenching induced by gold nanoparticles having different particle sizes. Fluorescence spectra clearly show that the quenching efficiency decreases with increasing size of the gold nanoparticles and increasing the distance between dye and nanoparticles. The mechanism of size- and distant-dependent fluorescence quenching has been discussed. Effects of various influential experimental parameters and configurations were investigated in order to optimize and miniaturize the sensor performance.

A gold-nanoparticle-based fluorescence resonance energy transfer probe for multiplexed hybridization detection : accurate identification of bio-agents DNA

We report a gold-nanoparticle-based miniaturized, inexpensive and battery-operated ultra-sensitive fluorescence resonance energy transfer (FRET) probe for screening biological agents DNA at the femtomolar level. We demonstrate a hybridization detection method using multicolor oligonucleotide-functionalized organic dyes and gold nanoparticles as nanoprobes. In the presence of various target sequences, detection of sequence-specific DNA is possible via an independent hybridization process. As proof of concept, multiplexed detection of two target sequences, (1)?oligonucleotide sequence associated with the anthrax lethal factor and (2) sequence related to positions 1027?1057 of the E.?coli 23S rDNA, have been demonstrated with high sensitivity and specificity. The quenching efficiency as a function of distance is investigated. The mechanism of distant dependence fluorescence quenching has been discussed.

Retention of latex colloids on calcite as a function of surface roughness and topography.

Adhesion of colloidal particles to mineral and rock surfaces is important for environmental and technological processes. Surface topography variations of mineral and rock surfaces at the submicrometer scale may play a significant role in colloid retention in the environment. Here, we present colloid deposition data on calcite as a function of submicrometer surface roughness based on surface data over a field of view of several square millimeters, sufficient to trace the pattern of common inhomogeneities on mineral surfaces. A freshly cleaved calcite crystal was reacted to produce a well-defined etch pit density of approximately 3.4 +/- 1.2 to 8.3 +/- 1.6 [10(-3) microm(-2)] and etch pit depth ranging from approximately 4 to 50 nm. This surface was exposed at the point of zero charge (PZC) of calcite to a colloidal suspension. We used a bimodal particle size distribution of nonfunctionalized polystyrene latex spheres with average diameters of 499 and 903 nm. Vertical scanning interferometry (VSI) was applied to quantify calcite surface topography variations as well as the retention of latex colloids. For both particle sizes, the experiments showed a positive correlation between the surface roughness (Rq) and the number of adsorbed particles. Etch pits were preferred sites for colloidal deposition in contrast to surface steps. The majority of adsorbed particles were trapped at etch pit walls compared to etch pit bottoms. Increasing pit density (D) and depth (d) resulted in an increase of colloidal retention. Deposition of smaller particles exceeded that of the larger-sized fraction of the bimodal system investigated here. Our results show that colloidal deposition at rough mineral and rock surfaces is an important geochemical process. The results about surface roughness dependent particle adsorption will foster the understanding and predictability of colloidal retention for a multitude of natural and technical processes.

Deposition of Latex Colloids at Rough Mineral Surfaces: An Analogue Study Using Nanopatterned Surfaces

Deposition of latex colloids on a structured silicon surface was investigated. The surface with well-defined roughness and topography pattern served as an analogue for rough mineral surfaces with half-pores in the submicrometer size. The silicon topography consists of a regular pit pattern (pit diameter = 400 nm, pit spacing = 400 nm, pit depth = 100 nm). Effects of hydrodynamics and colloidal interactions in transport and deposition dynamics of a colloidal suspension were investigated in a parallel plate flow chamber. The experiments were conducted at pH ∼ 5.5 under both favorable and unfavorable adsorption conditions using carboxylate functionalized colloids to study the impact of surface topography on particle retention. Vertical scanning interferometry (VSI) was applied for both surface topography characterization and the quantification of colloidal retention over large fields of view. The influence of particle diameter variation (d = 0.3-2 μm) on retention of monodisperse as well as polydisperse suspensions was studied as a function of flow velocity. Despite electrostatically unfavorable conditions, at all flow velocities, an increased retention of colloids was observed at the rough surface compared to a smooth surface without surface pattern. The impact of surface roughness on retention was found to be more significant for smaller colloids (d = 0.3, 0.43 vs. 1, 2 μm). From smooth to rough surfaces, the deposition rate of 0.3 and 0.43 μm colloids increased by a factor of ∼2.7 compared to a factor of 1.2 or 1.8 for 1 and 2 μm colloids, respectively. For a substrate herein, with constant surface topography, the ratio between substrate roughness and radius of colloid, Rq/rc, determined the deposition efficiency. As Rq/rc increased, particle-substrate overall DLVO interaction energy decreased. Larger colloids (1 and 2 μm) beyond a critical velocity (7 × 10(-5) and 3 × 10(-6) m/s) (when drag force exceeds adhesion force) tend to detach from the surface irrespective of the impact of roughness. For polydisperse solutions, an increase in the polydispersity and flow velocity resulted in a reduction of colloid deposition efficiency due to the resulting enhanced double-layer repulsion. Quantification of surface topography variations of two endmembers of natural grain surfaces showed that half-pore depths and roughness of sedimentary quartz grains are mainly in the micrometer range. Grains with diagenetically formed quartz overgrowths, however, show surface roughness mainly in the submicrometer range. Thus, surface topography features applied in the here presented analogue study and resulting variation in particle retention can serve as quantitative analogue for particle reactions in diagenetically altered quartz sands and sandstones. The reported impact of particle polydispersity can have an important application for quantitative prediction of retention of varying types of minerals, such as different clay minerals in the environment under prevailing unfavorable conditions.

Site-specific retention of colloids at rough rock surfaces.

The spatial deposition of polystyrene latex colloids (d = 1 μm) at rough mineral and rock surfaces was investigated quantitatively as a function of Eu(III) concentration. Granodiorite samples from Grimsel test site (GTS), Switzerland, were used as collector surfaces for sorption experiments. At a scan area of 300 × 300 μm(2), the surface roughness (rms roughness, Rq) range was 100-2000 nm, including roughness contribution from asperities of several tens of nanometers in height to the sample topography. Although, an increase in both roughness and [Eu(III)] resulted in enhanced colloid deposition on granodiorite surfaces, surface roughness governs colloid deposition mainly at low Eu(III) concentrations (≤5 × 10(-7) M). Highest deposition efficiency on granodiorite has been found at walls of intergranular pores at surface sections with roughness Rq = 500-2000 nm. An about 2 orders of magnitude lower colloid deposition has been observed at granodiorite sections with low surface roughness (Rq < 500 nm), such as large and smooth feldspar or quartz crystal surface sections as well as intragranular pores. The site-specific deposition of colloids at intergranular pores is induced by small scale protrusions (mean height = 0.5 ± 0.3 μm). These protrusions diminish locally the overall DLVO interaction energy at the interface. The protrusions prevent further rolling over the surface by increasing the hydrodynamic drag required for detachment. Moreover, colloid sorption is favored at surface sections with high density of small protrusions (density (D) = 2.6 ± 0.55 μm(-1), asperity diameter (φ) = 0.6 ± 0.2 μm, height (h) = 0.4 ± 0.1 μm) in contrast to surface sections with larger asperities and lower asperity density (D = 1.2 ± 0.6 μm(-1), φ = 1.4 ± 0.4 μm, h = 0.6 ± 0.2 μm). The study elucidates the importance to include surface roughness parameters into predictive colloid-borne contaminant migration calculations.

Miniaturized Sensor for Microbial Pathogens DNA and Chemical Toxins

A miniaturized, inexpensive and battery operated ultra-sensitive nanomaterial-based fluorescence resonance energy transfer (NSET) probe has been developed and evaluated for screening microbial pathogens DNA and chemical toxins at high sensitivity and selectivity. This paper illustrates application of the NSET portable device to detect microbial pathogens, e.g., Campylobacter, C. perfringens, and S. aureus DNA based on quenching of the NSET signal by gold nanoparticles to detect single base-mismatch DNA with high sensitivity (600 fM). Presence of the fluorescence signal indicates that the target DNA has been detected. We also report that the NSET probe is capable of screening chemical toxins like mercury from contaminated water with excellent sensitivity (2 parts-per-trillion) and selectivity for over competing analytes.

Deposition of mineral colloids on rough rock surfaces

Deposition of colloids on mineral and rock surfaces is an important mechanism to alter surface reactivity and to govern contaminant migration. Particle retention in aquifers occurs predominantly under electrostatically unfavorable conditions owing to the prevailing negative charge of both mineral colloids and rock surfaces. Mineral and rock surfaces show often an irregular surface topography and roughness variations over several orders of magnitude. This complicates the colloid-surface attachment predictability and results in poor understanding towards retention efficiency. Here we study the impact of submicron-scale morphology on the interaction between rock surfaces and mineral colloids. Colloid retention experiments using micrite surfaces were performed under electrostatically unfavorable conditions. Results showed a positive and linear correlation between adsorbed particle density and surface roughness (RMS roughness <100 nm). The existence of a minimum roughness range, required for initial colloid deposition was detected. Deposition occurred mainly at micrite grain boundaries that acted as surface steps. Linear deposition kinetics was found at constant flow rates. The site-specific impact of surface roughness was studied using nanostructured silicon wafer surfaces as a well-defined analog material. Experimental results from deposition on such surfaces suggest that the surface step density on collector surfaces is a critical parameter for quantitative prediction of colloid deposition. The importance of colloidal retention is highlighted for the diagenetic evolution of rocks, especially due to inhibition mechanisms that has consequences for cement mineral distribution and concentration as well as resulting reservoir quality. For further quantitative prediction and modeling of retention on rock surfaces, we suggest the application of an energy potential function that includes beside DLVO contribution the impact of particle kinetic energy (via fluid-flow velocity) as well as the impact of reactive site density (via surface roughness parameter data).