Guokun Liu

Quantitative super-resolution imaging uncovers reactivity patterns on single nanocatalysts

Metal nanoparticles are used as catalysts in a variety of important chemical reactions, and can have a range of different shapes, with facets and sites that differ in catalytic reactivity. To develop better catalysts it is necessary to determine where catalysis occurs on such nanoparticles and what structures are more reactive. Surface science experiments or theory can be used to predict the reactivity of surfaces with a known structure, and the reactivity of nanocatalysts can often be rationalized from a knowledge of their well-defined surface facets. Here, we show that a knowledge of the surface facets of a gold nanorod catalyst is insufficient to predict its reactivity, and we must also consider defects on the surface of the nanorod. We use super-resolution fluorescence microscopy to quantify the catalysis of the nanorods at a temporal resolution of a single catalytic reaction and a spatial resolution of ∼40xa0nm. We find that within the same surface facets on the sides of a single nanorod, the reactivity is not constant and exhibits a gradient from the centre of the nanorod towards its two ends. Furthermore, the ratio of the reactivity at the ends of the nanorod to the reactivity at the sides varies significantly from nanorod to nanorod, even though they all have the same surface facets.

Electrostatic Interaction Based Approach to Thrombin Detection by Surface-Enhanced Raman Spectroscopy

We have developed an electrostatic interaction based biosensor for thrombin detection using surface-enhanced Raman spectroscopy (SERS). This method utilized the electrostatic interaction between capture (thrombin aptamer) and probe (crystal violet, CV) molecules. The specific interaction between thrombin and aptamer could weaken the electrostatic barrier effect from the negative charged aptamer SAMs to the diffusion process of the positively charged CV from the bulk solution to the Au nanoparticle surface. Therefore, the more the bound thrombin, the more the CV molecules near the Au nanoparticle surface and the stronger the observed Raman signal of CV, provided the Raman detections were set at the same time point for each case. This procedure presented a highly specific selectivity and a linear detection of thrombin in the range from 0.1 nM to 10 nM with a detection limit of about 20 pM and realized the thrombin detection in human blood serum solution directly. The electrostatic interaction based technique provides an easy and fast-responding optical platform for a signal-on detection of proteins, which might be applicable for the real time assay of proteins.

A New Aptameric Biosensor for Cocaine Based on Surface‐Enhanced Raman Scattering Spectroscopy

The present study reports the proof of principle of a reagentless aptameric sensor based on surface-enhanced Raman scattering (SERS) spectroscopy with signal-on architecture using a model target of cocaine. This new aptameric sensor is based on the conformational change of the surface-tethered aptamer on a binding target that draws a certain Raman reporter in close proximity to the SERS substrate, thereby increasing the Raman scattering signal due to the local enhancement effect of SERS. To improve the response performance, the sensor is fabricated from a cocaine-templated mixed self-assembly of a 3-terminal tetramethylrhodamine (TMR)-labeled DNA aptamer on a silver colloid film by means of an alkanethiol moiety at the 5 end. This immobilization strategy optimizes the orientation of the aptamer on the surface and facilitates the folding on the binding target. Under optimized assay conditions, one can determine cocaine at a concentration of 1 muM, which compares favorably with analogous aptameric sensors based on electrochemical and fluorescence techniques. The sensor can be readily regenerated by being washed with a buffer. These results suggest that the SERS-based transducer might create a new dimension for future development of aptameric sensors for sensitive determination in biochemical and biomedical studies.

Single-Molecule Catalysis Mapping Quantifies Site-Specific Activity and Uncovers Radial Activity Gradient on Single 2D Nanocrystals

Shape-controlled metal nanocrystals are a new generation of nanoscale catalysts. Depending on their shapes, these nanocrystals exhibit various surface facets, and the assignments of their surface facets have routinely been used to rationalize or predict their catalytic activity in a variety of chemical transformations. Recently we discovered that for 1-dimensional (1D) nanocrystals (Au nanorods), the catalytic activity is not constant along the same side facets of single nanorods but rather differs significantly and further shows a gradient along its length, which we attributed to an underlying gradient of surface defect density resulting from their linear decay in growth rate during synthesis (Nat. Nanotechnol.2012, 7, 237-241). Here we report that this behavior also extends to 2D nanocrystals, even for a different catalytic reaction. By using super-resolution fluorescence microscopy to map out the locations of catalytic events within individual triangular and hexagonal Au nanoplates in correlation with scanning electron microscopy, we find that the catalytic activity within the flat {111} surface facet of a Au nanoplate exhibits a 2D radial gradient from the center toward the edges. We propose that this activity gradient results from a growth-dependent surface defect distribution. We also quantify the site-specific activity at different regions within a nanoplate: The corner regions have the highest activity, followed by the edge regions and then the flat surface facets. These discoveries highlight the spatial complexity of catalytic activity at the nanoscale as well as the interplay amid nanocrystal growth, morphology, and surface defects in determining nanocatalyst properties.

Single-molecule electrocatalysis by single-walled carbon nanotubes.

We report a single-molecule fluorescence study of electrocatalysis by single-walled carbon nanotubes (SWNTs) at single-reaction resolution. Applying super-resolution optical imaging, we find that the electrocatalysis occurs at discrete, nanometer-dimension sites on SWNTs. Single-molecule kinetic analysis leads to an electrocatalytic mechanism, allowing quantification of the reactivity and heterogeneity of individual reactive sites. Combined with conductivity measurements, this approach will be powerful to interrogate how the electronic structure of SWNTs affects the electrocatalytic interfacial charge transfer, a process fundamental to photoelectrochemical cells.

How Does a Single Pt Nanocatalyst Behave in Two Different Reactions? A Single-Molecule Study

Using single-molecule microscopy of fluorogenic reactions we studied Pt nanoparticle catalysis at single-particle, single-turnover resolution for two reactions: one an oxidative N-deacetylation and the other a reductive N-deoxygenation. These Pt nanoparticles show distinct catalytic kinetics in these two reactions: one following noncompetitive reactant adsorption and the other following competitive reactant adsorption. In both reactions, single nanoparticles exhibit temporal activity fluctuations attributable to dominantly spontaneous surface restructuring. Depending on the reaction sequence, single Pt nanoparticles may or may not show activity correlations in catalyzing both reactions, reflecting the structure insensitivity of the N-deacetylation reaction and the structure sensitivity of the N-deoxygenation reaction.

Laser-induced chemical transformation of PATP adsorbed on Ag nanoparticles by surface-enhanced Raman spectroscopy-a study of the effects from surface morphology of substrate and surface coverage of PATP.

The laser induced transformation of p-aminothiophenol (PATP) to p,p-dimercaptoazobenzene (DMAB) has attracted intensive interest recently, in which localized surface plasmon resonance (LSPR) assisted photocatalysis has been demonstrated to play an important role. In this paper, we systematically investigate the factors that influence the reaction for further understanding the mechanism using surface-enhanced Raman spectroscopy. The laser-induced formation of DMAB was found to depend on the surface coverage of PATP, the aggregation state of NPs, and the laser power. The disappearance of DMAB Raman signal at very low concentration of Ag NPs reveals that DMAB may only be formed between the neighboring NPs that can provide a suitable distance for the interaction between adsorbed PATP molecules.

Different behaviors in the transformation of PATP adsorbed on Ag or Au nanoparticles investigated by surface-enhanced Raman spectroscopy – A study of the effects from laser energy and annealing

In order to explore the key role of surface plasmon resonance (SPR) and active (3)O2 for the chemical transformation to 4,4-dimercaptoazobenzene (DMAB) from p-aminothiophenol (PATP) adsorbed on Ag or Au NPs, we systematically investigated the laser wavelength and temperature dependent surface-enhanced Raman spectra of PATP capped Ag and Au NPs. DMAB can be easily observed at the 514.5nm laser for Ag NPs but at the 632.8nm laser for Au NPs, indicating that a suitable energy level is necessary for the formation of DMAB. The tendency is consistent with the wavelength dependent SPR properties of Ag or Au NPs accordingly. With the energy provided by annealing, the transformation of PATP to DMAB is much easier on Ag NPs at a lower temperature, and more DMAB can be observed at the same temperature, compared to the case of Au NPs under the same condition. It is mainly due to the active (3)O2 on Ag surfaces could be more easily formed than that on Au surfaces.

An auto-adaptive background subtraction method for Raman spectra

Background subtraction is a crucial step in the preprocessing of Raman spectrum. Usually, parameter manipulating of the background subtraction method is necessary for the efficient removal of the background, which makes the quality of the spectrum empirically dependent. In order to avoid artificial bias, we proposed an auto-adaptive background subtraction method without parameter adjustment. The main procedure is: (1) select the local minima of spectrum while preserving major peaks, (2) apply an interpolation scheme to estimate background, (3) and design an iteration scheme to improve the adaptability of background subtraction. Both simulated data and Raman spectra have been used to evaluate the proposed method. By comparing the backgrounds obtained from three widely applied methods: the polynomial, the Baeks and the airPLS, the auto-adaptive method meets the demand of practical applications in terms of efficiency and accuracy.

Developing on-site paper colorimetric monitoring technique for quick evaluating copper ion concentration in mineral wastewater

With the reinforce of the copper mining, the on-site monitoring of the accompanied effluent discharge is highly demanded for the emergency response to minimize the negative effect of the effluent on the surrounding ecosystem. On the basis of the specific interaction between Cu2+ and l-Cysteine (l-Cys), which was modified on gold nanoparticles (Au NPs), and the aggregation dependent surface plasmon resonance (SPR) of Au NPs, we developed an easy-on-going paper colorimetric method for the quick evaluating the copper ion concentration in the waste water excreted from the copper mine. The color change of l-Cys modified Au NPs (l-Cys-Au NPs)immobilized on a filter paper was very sensitive to the Cu2+ concentration and free of interference from other metal ions typically in waste water. The proposed paper colorimetry has the LOD of 0.09mg/L and the linear range of 0.1-10mg/L, respectively, with the RSD (n=5) was 6.6% for 1mg/L Cu2+ and 3.5% for 5mg/L Cu2+. The quantitative analysis results for the mineral wastewater is in good agreement the China National Environmental Protection Standards HJ485-2009, which indicates the current method could be developed to the on-site detection technique for the emergency response in monitoring Cu2+ in industrial wastewater or polluted water.