Abdul Rahim Ferhan

Oriented Gold Nanoparticle Aggregation for Colorimetric Sensors with Surprisingly High Analytical Figures of Merit

The common drawbacks of current colorimetric sensors using gold nanoparticle aggregation is its relatively low sensitivity and narrow dynamic range, which restrict their application in real sample analysis when competing with other analytical techniques such as fluorescence and chemiluminescence. In this article, we demonstrate a novel strategy to construct colorimetric sensors based on gold nanoparticle aggregation. Unlike the conventional colorimetric sensors which cause the formation of large nanoparticle aggregates, in our strategy, dimers are selectively formed upon target binding, which results in significantly improved long-term stability and a more than 2 orders of magnitude wider dynamic range of detection than that of the conventional colorimetric sensors. In addition, a strategy to minimize the interparticle gap through the formation of a Y-shaped DNA duplex enables to increase the limit of detection by 10,000 times. The analytical figures of merit of the proposed sensor are comparable to those of the fluorescence-based sensors.

Nanoarray-based biomolecular detection using individual Au nanoparticles with minimized localized surface plasmon resonance variations.

Here, we present a mean to expand the use of individual metallic nanoparticles to two-dimensional plasmonic nanoarrays. An optical detection platform to track down localized surface plasmon resonance (LSPR) signals of individual nanoparticles on substrates was built for the application of plasmonic nanoarrays. A pseudoimage of nanoparticles on a substrate was reconstructed from their scattering spectra obtained by scanning a user-defined area. The spectral and spatial resolutions of the system were also discussed in detail. Most importantly, we present a method to normalize the localized surface plasmon resonance from geometrically different nanoparticles. After normalization, plasmonic responses from different particles become highly consistent, creating well-fitted dose-response curves of both surrounding refractive index changes and receptor-analyte binding to the surface of individual nanoparticles. Finally, the proof-of-concept system for plasmonic nanoarray detection is demonstrated by the measurement of the aptamer-thrombin binding event.

Solid-phase colorimetric sensor based on gold nanoparticle-loaded polymer brushes: lead detection as a case study.

We introduce a novel solid-phase colorimetric sensor facilely fabricated by loading unmodified gold nanoparticles into poly(oligo(ethylene glycol)methacrylate) (POEGMA) brushes grown on glass. Our work reports the first synergistic combination of metallic nanoparticles acting as a colorimetric sensing module with a nonfouling polymer matrix acting both as a nonrigid scaffold and a screen to reduce interference from nontarget molecules. In addition, as the nanocomposite is formed on a transparent substrate, solid-phase detection can be performed in the same manner as in the solution-phase. We demonstrate the use of this unique platform for label-free lead detection based on the release of gold nanoparticles from the polymer brush upon exposure to lead ions. An ultralow limit-of-detection of 25 pM (S/N = 3) and a dynamic range of 100 pM to 100 nM (R(2) = 0.987) are achieved. Furthermore, the detection is up to 1000-fold more selective to lead over other common heavy metal ions.

Distance‐Mediated Plasmonic Dimers for Reusable Colorimetric Switches: A Measurable Peak Shift of More than 60 nm

The first reconfigurable colorimetric DNA switches based on target DNA binding are reported. This DNA binding actuates a change in the interparticle distance between gold nanoparticle dimers. A significant spectral shift of 68 nm is achievable from on-off switching. The reconfigurability is possible owing to thiol and EDC-imidazole coupling which anchors the DNA linkers to the nanoparticles. The huge spectral shift allows the unaided eye to observe single target biomolecular binding event in real time under a darkfield microscope. The limit-of-detection for target molecules in PBS and human serum are 10(-13) M and 10(-11) M respectively. An improved fabrication strategy via asymmetric functionalization is also described, assisted by solid phase synthesis which minimizes the formation of trimers and multimers.

Influence of ionic strength and surfactant concentration on electrostatic surfacial assembly of cetyltrimethylammonium bromide-capped gold nanorods on fully immersed glass.

The effect of ionic strength as well as surfactant concentration on the surface assembly of cetyltrimethylammonium bromide (CTAB)-capped gold nanorods (GNRs) has been studied. Glass substrates were modified to yield a net negative charge through electrostatic coating of polystyrenesulfonate (PSS) over a self-assembled monolayer (SAM) of positively charged aminopropyltriethoxysilane (APTS). The substrates were then fully immersed in GNR solutions at different CTAB concentrations and ionic strengths. Under slightly excess CTAB concentrations, it was observed that the density of GNRs immobilized on a substrate was predictably tunable through the adjustment of NaCl concentration over a wide range. Motivated by the experimental observation, we hypothesize that electrostatic shielding of charges around the GNRs affects the density of GNR immobilization. This model ultimately explains that at moderate to high CTAB concentrations a second electrostatic shielding effect contributed by excess CTAB molecules occurs, resulting in a parabolic trend of nanorod surface density when ionic strength is continually increased. In contrast, at a low CTAB concentration, the effect of ionic strength becomes much less significant due to insufficient CTAB molecules to provide for the second electrostatic shielding effect. The tunability of electrostatic-based surface assembly of GNRs enables the attainment of a dense surface assembly of nanorods without significant removal of CTAB or any other substituted stabilizing agent, both of which could compromise the stability and morphology of GNRs in solution. An additional study performed to investigate the robustness of such electrostatic-based surface assembly also proved its reliability to be used as biosensing platforms.

Tunable scattered colors over a wide spectrum from a single nanoparticle

By controlling the thickness of the silver shell, Au-Ag core-shell nanorods with quadruple plasmonic peaks corresponding to red, green, violet and deep violet regions have been prepared. Additionally, under polarized light, we achieved tunability of scattered colors from a single nanoparticle over an exceptionally wide wavelength range. The observed colors include red, orange, yellow, green, blue and purple.

In-stacking: a strategy for 3D nanoparticle assembly in densely-grafted polymer brushes

We introduce a facile strategy to obtain dense 3-dimensional assembly of non-functionalized gold nanoparticles into unmodified, end-tethered poly(oligo(ethylene glycol) methacrylate) bottle brushes of high grafting densities. Referred to as ‘in-stacking’, we present its mechanism based on evidence from UV-vis absorbance, AFM and FESEM.

Quantitative Profiling of Nanoscale Liposome Deformation by a Localized Surface Plasmon Resonance Sensor.

Characterizing the shape of sub-100 nm, biological soft-matter particulates (e.g., liposomes and exosomes) adsorbed at a solid-liquid interface remains a challenging task. Here, we introduce a localized surface plasmon resonance (LSPR) sensing approach to quantitatively profile the deformation of nanoscale, fluid-phase 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) liposomes contacting a titanium dioxide substrate. Experimental and theoretical results validate that, due to its high sensitivity to the spatial proximity of phospholipid molecules near the sensor surface, the LSPR sensor can discriminate fine differences in the extent of ionic strength-modulated liposome deformation at both low and high surface coverages. By contrast, quartz crystal microbalance-dissipation (QCM-D) measurements performed with equivalent samples were qualitatively sensitive to liposome deformation only at saturation coverage. Control experiments with stiffer, gel-phase 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) liposomes verified that the LSPR measurement discrimination arises from the extent of liposome deformation, while the QCM-D measurements yield a more complex response that is also sensitive to the motion of adsorbed liposomes and coupled solvent along with lateral interactions between liposomes. Collectively, our findings demonstrate the unique measurement capabilities of LSPR sensors in the area of biological surface science, including competitive advantages for probing the shape properties of adsorbed, nanoscale biological particulates.

Integration of Quartz Crystal Microbalance-Dissipation and Reflection-Mode Localized Surface Plasmon Resonance Sensors for Biomacromolecular Interaction Analysis

The combination of label-free, surface-sensitive measurement techniques based on different physical principles enables detailed characterization of biomacromolecular interactions at solid-liquid interfaces. To date, most combined measurement systems have involved experimental techniques with similar probing volumes, whereas the potential of utilizing techniques with different surface sensitivities remains largely unexplored, especially for data interpretation. Herein, we report a combined measurement approach that integrates a conventional quartz crystal microbalance-dissipation (QCM-D) setup with a reflection-mode localized surface plasmon (LSPR) sensor. Using this platform, we investigate vesicle adsorption on a titanium oxide-coated sensing substrate along with the amphipathic, α-helical (AH) peptide-induced structural transformation of surface-adsorbed lipid vesicles into a supported lipid bilayer (SLB) as a model biomacromolecular interaction. While the QCM-D and LSPR signals both detected mass uptake arising from vesicle adsorption, tracking the AH peptide-induced structural transformation revealed more complex measurement responses based on the different surface sensitivities of the two techniques. In particular, the LSPR signal recorded an increase in optical mass near the sensor surface which indicated SLB formation, whereas the QCM-D signals detected a significant loss in net acoustic mass due to excess lipid and coupled solvent leaving the probing volume. Importantly, these measurement capabilities allowed us to temporally distinguish the process of SLB formation at the sensor surface from the overall structural transformation process. Looking forward, these label-free measurement capabilities to simultaneously probe adsorbates at multiple length scales will provide new insights into complex biomacromolecular interactions.

In situ synthesis of protein-resistant poly(oligo(ethylene glycol)methacrylate) films in capillary for protein separation

We report a method to modify a silica capillary with poly(oligo(ethylene glycol)methacrylate) (POEGMA) and its performance for protein separation. We optimized the grafting density and thickness of the POEGMA film and investigated the effect of running buffer pH, ionic strength, separation voltage, and sample injection time. The POEGMA-coated capillary was successfully utilized for the separation of six model proteins. Under optimized conditions, the resolution was found to be much better than a bare capillary, and even better than a widely used, commercially available PEG-modified capillary.