Improved Photocatalytic Performance of TiO2-Nitrogen-Doped Graphene Quantum Dot Composites Mediated by Heterogeneous Interactions.

Photocatalysis is typically monitored via analysis of phases in isolation and focuses on the removal of a target analyte from the solution phase. Here we analyze the photocatalytic action of a TiO2-nitrogen-doped graphene quantum dot (NGQD) composite on a target analyte, phenol, using comprehensive multiphase NMR (CMP-NMR) which observes signals in solid, solution, and gel phases in situ. Phenol preferentially interacts with the composite photocatalyst compared to pure TiO2, increasing its effective concentration near the catalyst surface and its degradation rate. The presence of NGQDs in the composite reduced the fouling of the catalyst surface and caused a reduction of photogenerated intermediates. Increased heterogeneous interactions, likely mediated by π-π interactions, are hypothesized to cause each of these improvements in the observed photocatalytic performance by TiO2-NGQDs. CMP-NMR allows the elucidation of how the photocatalytic mechanism is enhanced via material design and provides a foundation for the development of efficient photocatalysts.

TiO2-NGQD composite photocatalysts with switchable photocurrent response.

A series of titanium dioxide-nitrogen doped graphene quantum dot (TiO2-NGQD) composite photocatalysts were synthesized through a simple hydrothermal reaction with varied NGQD content. Through a proposed Z-Scheme heterojunction, the composites were able to achieve increased photocurrent generation and photocatalytic degradation of phenol under both full spectrum and visible only illumination. The prepared composites were able to switch from anodic to cathodic photocurrent by changing the light source from full spectrum to visible wavelengths. The photocatalytic capabilities of the composites were tested by degrading phenol and this was monitored via nuclear magnetic resonance. All composites outperformed the commercial standard P25 TiO2 under both full spectrum and visible irradiation, with the 8 wt% NGQD composite showing a visible improvement of over 600% compared to P25. With the ability to manipulate the generation of majority charge carriers, TiO2-NGQDs have significant potential not only in photocatalysis, but in far reaching applications such as energy harvesting and water splitting.

A new perspective on the photocatalytic action of titanium dioxide on phenol elucidated using comprehensive multiphase NMR.

Comprehensive Multiphase NMR (CMP-NMR) is a recently developed technique capable of simultaneously observing different phases - solutions, gels, and solids - while providing the chemical specificity of traditional NMR. With this new tool, the heterogeneous photocatalysis of phenol by titanium dioxide (P25 TiO2) is re-examined to gain information about the occurrence of reaction at different regions between the catalyst and the solution. It was found that the proportion of phenol in different phases changes over the course of the photodegradation period. The photocatalyst appears to preferentially degrade phenol molecules that are weakly associated with the surface, such that they have restricted mobility in a 'gel-like' state. Diffusion Ordered Spectroscopy (DOSY) corroborates the relative change in phenol signals between freely diffusing solution and diffusion restricted gels as measured using CMP-NMR. The surface of P25 TiO2 was found to foul over the course of the 200-hour photodegradation period that was monitored using the solid-state capabilities of the CMP-NMR. Finally, CMP-NMR showed differences in the photodegradation of phenol by P25 TiO2 to that of a TiO2-nitrogen doped graphene quantum dot (NGQD) composite. With the latter composite, no fouling of the surface was seen over time. This application of CMP-NMR to the field of catalysis demonstrates its potential to better understand and study photocatalytic systems in general.

Anchoring gold nanoparticles on poly(3,4-ethylenedioxythiophene) (PEDOT) nanonet as three-dimensional electrocatalysts toward ethanol and 2-propanol oxidation.

Renewable alcohol oxidation is of vital significance for clean energy conversion and storage. Here, we fabricated a three-dimensional (3D) nanonet-like hybrid catalyst combining Au nanoparticles and poly(3,4-ethylenedioxythiophene) (PEDOT) together, in which PEDOT nanonets act as the framework of the 3D catalyst and the support for the dispersion of Au nanoparticles. The catalyst was designated as Au-PEDOT. By using conductive carbon cloth (CC) as electrode substrates, the as-fabricated Au-PEDOT/CC electrodes were applied to evaluate the electrocatalytic activity towards ethanol and 2-propanol in the alkaline media, respectively. The catalytic activity on Au-PEDOT/CC in terms of the peak current and/or peak current density towards ethanol and 2-propanol oxidation is five times higher than that on comparative Au/CC catalysts, respectively, which is also higher than that on some similar materials reported in the literature. In addition, the Au-PEDOT/CC electrode also possessed great durability and reproducibility. This enhancement in electrocatalytic activity can be attributed to a number of factors: the nano-scale of the Au catalysts, the 3D nanostructure of the catalysts, the conductivity of PEDOT, as well as the effect of alkaline media. These results indicate the as-synthesized Au-PEDOT is a promising electrocatalyst for liquid fuel oxidation.

Ultra-stable Electrochemical Sensor for Detection of Caffeic Acid Based on Platinum and Nickel Jagged-Like Nanowires.

Electrochemical sensors have the high sensitivity, fast response, and simple operation for applications in biological, medical, and chemical detection, but limited by the poor stability and high cost of the electrode materials. In this work, we used PtNi lagged-like nanowire for caffeic acid (CA) electrochemical detection. The removal of outer layer Ni during reaction process contributed to the rehabilitation of active Pt sites at the surface, leading to the excellent electrocatalytic behavior of CA sensing. Carbon-supported PtNi-modified glassy carbon electrode (PtNi/C electrode) showed a broad CA detecting range (from 0.75 to 591.783 µM), a low detection limit (0.5 µM), and excellent stability. The electrode preserved high electrocatalytic performance with 86.98% of the initial oxidation peak current retained after 4000 potential cycles in 0.5 mM caffeic acid solution. It also demonstrates excellent anti-interference capability and is ready for use in the real sample analysis.

Whole-field macro- and micro-deformation characteristic of unbound water-loss in dentin hard tissue.

High-resolution deformation measurements in a functionally graded hard tissue such as human dentin are essential to understand the unbound water-loss mediated changes and their role in its mechanical integrity. Yet a whole-field, 3-dimensional (3D) measurement and characterization of fully hydrated dentin in both macro- and micro-scales remain to be a challenge. This study was conducted in 2 stages. In stage-1, a stereo-digital image correlation approach was utilized to determine the water-loss and load-induced 3D deformations of teeth in a sagittal section over consecutively acquired frames, from a fully hydrated state to nonhydrated conditions for a period up to 2 hours. The macroscale analysis revealed concentrated residual deformations at the dentin-enamel-junction and the apical regions of root in the direction perpendicular to the dentinal tubules. Significant difference in the localized deformation characteristics was observed between the inner and outer aspects of the root dentin. During quasi-static loadings, further increase in the residual deformation was observed in the dentin. In stage-2, dentin microstructural variations induced by dynamic water-loss were assessed with environmental scanning electron microscopy and atomic force microscopy (AFM), showing that the dynamic water-loss induced distention of dentinal tubules with concave tubular edges, and concurrent contraction of intertubular dentin with convex profile. The findings from the current macro- and micro-scale analysis provided insight on the free-water-loss induced regional deformations and ultrastructural changes in human dentin.

High Efficiency Photoelectrocatalytic Methanol Oxidation on CdS Quantum Dots Sensitized Pt Electrode.

A cadmium sulfide quantum dots sensitized Pt (Pt-CdS) composite was synthesized using a solvothermal method and characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-vis diffuse reflectance spectroscopy. The catalytic properties of the as-prepared electrode for methanol oxidation were evaluated by cyclic voltammetry (CV), chronoamperometry, electrochemical impedance spectrum (EIS) and photocurrent responses. The as-prepared Pt-CdS electrode displayed a significant enhancement in the electrocatalytic activity and stability for methanol oxidation in the presence of visible light irradiation. The synergistic effect of both the electro- and photocatalytic reaction contributes to this enhanced catalytic performance. Our result suggests a new paradigm to construct photoelectrocatalysts with high performance and good stability for direct methanol fuel cells with the assistance of visible-light illumination.

Angiopoietin-1 peptide QHREDGS promotes osteoblast differentiation, bone matrix deposition and mineralization on biomedical materials.

Bone loss occurs as a consequence of a variety of diseases as well as from traumatic injuries, and often requires therapeutic intervention. Strategies for repairing and replacing damaged and/or lost bone tissue include the use of biomaterials and medical implant devices with and without osteoinductive coatings. The soluble growth factor angiopoietin-1 (Ang-1) has been found to promote cell adhesion and survival in a range of cell types including cardiac myocytes, endothelial cells and fibroblasts through an integrin-dependent mechanism. Furthermore, the short sequence QHREDGS has been identified as the integrin-binding sequence of Ang-1 and as a synthetic peptide has been found to possess similar integrin-dependent effects as Ang-1 in the aforementioned cell types. Integrins have been implicated in osteoblast differentiation and bone mineralization, processes critical to bone regeneration. By binding integrins on the osteoblast surface, QHREDGS could promote cell survival and adhesion, as well as conceivably osteoblast differentiation and bone mineralization. Here we immobilized QHREDGS onto polyacrylate (PA)-coated titanium (Ti) plates and polyethylene glycol (PEG) hydrogels. The osteoblast differentiation marker, alkaline phosphatase, peaked in activity 4-12 days earlier on the QHREDGS-immobilized PA-coated Ti plates than on the unimmobilized, DGQESHR (scrambled)- and RGDS-immobilized surfaces. Significantly more bone matrix was deposited on the QHREDGS-immobilized Ti surface than on the other surfaces as determined by atomic force microscopy. The QHREDGS-immobilized hydrogels also had a significantly higher mineral-to-matrix (M/M) ratio determined by Fourier transform infrared spectroscopy. Alizarin Red S and von Kossa staining and quantification, and environmental scanning electron microscopy showed that while both the QHREDGS- and RGDS-immobilized surfaces had extensive mineralization relative to the unimmobilized and DGQESHR-immobilized surfaces, the mineralization was more considerable on the QHREDGS-immobilized surface, both with and without the induction of osteoblast differentiation. Finally, treatment of cell monolayers with soluble QHREDGS was demonstrated to upregulate osteogenic gene expression. Taken together, these results demonstrate that the QHREDGS peptide is osteoinductive, inducing osteoblast differentiation, bone matrix deposition and mineralization.

In vitro synthesis of native, fibrous long spacing and segmental long spacing collagen.

Collagen fibrils are present in the extracellular matrix of animal tissue to provide structural scaffolding and mechanical strength. These native collagen fibrils have a characteristic banding periodicity of ~67 nm and are formed in vivo through the hierarchical assembly of Type I collagen monomers, which are 300 nm in length and 1.4 nm in diameter. In vitro, by varying the conditions to which the monomer building blocks are exposed, unique structures ranging in length scales up to 50 microns can be constructed, including not only native type fibrils, but also fibrous long spacing and segmental long spacing collagen. Herein, we present procedures for forming the three different collagen structures from a common commercially available collagen monomer. Using the protocols that we and others have published in the past to make these three types typically lead to mixtures of structures. In particular, unbanded fibrils were commonly found when making native collagen, and native fibrils were often present when making fibrous long spacing collagen. These new procedures have the advantage of producing the desired collagen fibril type almost exclusively. The formation of the desired structures is verified by imaging using an atomic force microscope.

Direct visualization of the formation of RecA/dsDNA complexes at the single-molecule level.

The assembly of RecA on linear dsDNA with ATPγS in the reaction was elucidated using atomic force microscopy (AFM) on a single-molecule level. It was found that assembly generally (∼95%) proceeded from a single nucleation site that started from one end of the DNA strand. About 5% of the complexes were formed starting either from both ends or from the middle of dsDNA strand. In all these cases, the RecA coating was contiguous for each region suggesting the binding of RecA to DNA is cooperative. The AFM observation provides direct experimental evidence to show how RecA binds to linear dsDNA in the presence of ATPγS.

Note: A scanning electron microscope sample holder for bidirectional characterization of atomic force microscope probe tips.

A novel sample holder that enables atomic force microscopy (AFM) tips to be mounted inside a scanning electron microscopy (SEM) for the purpose of characterizing the AFM tips is described. The holder provides quick and easy handling of tips by using a spring clip to hold them in place. The holder can accommodate two tips simultaneously in two perpendicular orientations, allowing both top and side view imaging of the tips by the SEM.

Direct evidence of the role of ATPγS in the binding of single-stranded binding protein (Escherichia coli) and RecA to single-stranded DNA.

To gain insight into the influence of ATPγS on the competitive binding of RecA and single-stranded binding protein (SSB) on single-stranded DNA (ssDNA), AFM imaging was used to examine the three-dimensional structures of the different complexes formed by the binding of the two proteins on ssDNA in the presence and absence of ATPγS. In the presence of ATPγS, RecA attaches to ssDNA, displacing SSB, to form continuous binding regions that caused considerable elongation of the strand. When ATPγS is absent, RecA could not compete with SSB and only binds at a few sites that correspond to the vacancy in ssDNA left when SSB unbinds. These results provide direct evidence that, while SSB binding affinity to DNA is substantially higher than that of RecA, the presence of ATPγS is sufficient to alter the events and enable RecA coating of DNA.

Direct visualization of the formation and structure of RecA/dsDNA complexes.

A direct visualization of the construction of RecA/DNA nucleofilament complexes was obtained using high-resolution atomic force microscopy (AFM). It showed that the complex consisted of helical loops, with each helical loop composed of units of size equivalent to approximately six monomers. The contour of stretched DNA that was embedded beneath RecA monomers was also observed directly. Images of RecA/DNA complexes showed both left- and right-handed helices, with a range of helical pitches. This was considered to imply that the complexes were flexible enough such that they are prone to compression forces that occur during sample preparation.

Combinatorial polyelectrolyte multilayer film fabrication.

A combinatorial strategy for the fabrication of a library of polyelectrolyte multilayer films is presented in this paper. This innovative approach involves the parallel formation of polyelectrolyte multilayer films in the individual wells of polystyrene microtitre plates under various deposition conditions. The progress of film formation was monitored via the intensity of the UV-vis absorbance of one of the depositing polyelectrolytes using a conventional microplate reader. We demonstrate the utility of this technique by building a library of 120 distinct polyelectrolyte multilayer films. Both the primer layer composition and salt content of the polyeletrolyte solutions were systematically varied in the preparation of films of nine bilayers. Film growth did not follow a linear adsorption regime for the first three bilayers regardless of the composition of the primer layer. We observed that increasing the sodium chloride concentration in the polyelectrolyte solutions resulted in increased polyelectrolyte absorption for all the conditions studied. The approach presented here is a convenient method of producing and characterizing multiple films rapidly and reproducibly, making it a valuable tool for optimizing film fabrication.

Potassium ion mediated collagen microfibril assembly on mica.

Potassium ion can critically effect the interaction between collagen microfibrils and mica leading to different ordered structures that vary dramatically with changing ion concentration. AFM images of the structures formed at different ion concentrations appear to be intermediate stages in the progression from disordered to ordered film. At 200 mM potassium ion concentration, a nanometer-thick array of aligned and bundled microfibrils covering large areas can be created easily and reproducibly on mica.

Direct and real-time visualization of the disassembly of a single RecA-DNA-ATPgammaS complex using AFM imaging in fluid.

RecA disassembly from circular double-stranded DNA (dsDNA) was studied by atomic force microscopy (AFM) imaging in fluid on a single molecule scale. The RecA/DNA complex was formed in the presence of ATPgammaS, and the disassembly was then initiated by buffer exchange to rinse off ATPgammaS. Performing AFM imaging in fluid allowed direct and real-time visualization of the disassembly of RecA from dsDNA in solution. It was found that RecA disassembly commenced from multiple sites both in deionized water and in buffer; the areas where RecA dissociated showed the appearance of "gaps" in the filamentous structure. RecA further disassembled either through the already existing "gaps" or by generation of new gaps. The disassembly was slower in buffer than in deionized water, suggesting that ions also contribute to the stabilization of the complex. RecA hexamers and monomers were observed in deionized water and in buffer, respectively, during the disassembly process.

Fibrous long spacing type collagen fibrils have a hierarchical internal structure.

Nanodissection of single fibrous long spacing (FLS) type collagen fibrils by atomic force microscopy (AFM) reveals hierarchical internal structure: Fibrillar subcomponents with diameters of approximately 10 to 20 nm were observed to be running parallel to the long axis of the fibril in which they are found. The fibrillar subcomponent displayed protrusions with characteristic approximately 270 nm periodicity, such that protrusions on neighboring subfibrils were aligned in register. Hence, the banding pattern of mature FLS-type collagen fibrils arises from the in-register alignment of these fibrillar subcomponents. This hierarchical organization observed in FLS-type collagen fibrils is different from that previously reported for native-type collagen fibrils, displaying no supercoiling at the level of organization observed.

Novel polymorphism of RecA fibrils revealed by atomic force microscopy.

RecA fibrils in physiological conditions have been successfully imaged using Tapping Mode atomic force microscopy. This represents the first time images of recA have been obtained without drying, freezing and/or exposure to high vacuum conditions. While previously observed structures - the monomer, the hexamer, the short rod - were seen, a new type of fibril was also observed. This protofibril is narrower in diameter than the standard fibril, and occurs in three distinct morphologies: aperiodic, 100-nm periodic, and 150-nm periodic. In addition, much longer rods were observed, and appear curved and even circular.

An enzyme-amplified diffraction-based immunoassay.

We have previously shown that a gold-conjugated secondary label can be used to reduce the limit of detection in a diffraction-based assay by more than 40-fold. We now show that by using a combination of a peroxidase-conjugated secondary label and a precipitating substrate the limit of detection in a diffraction-based assay can be reduced by more than 1000-fold. The response to secondary enhancement was linear for concentrations from 50 to 2000 pg/mL of antidigoxin.

DNA base pair resolution by single molecule force spectroscopy.

The forces that hold complementary strands of DNA together in a double helix, and the role of base mismatches in these, are examined by single molecule force spectroscopy using an atomic force microscope (AFM). These forces are important when considering the binding of proteins to DNA, since these proteins often mechanically stretch the DNA during their action. In AFM measurement of forces, there is an inherent instrumental limitation that makes it difficult to compare results from different experimental runs. This is circumvented by using an oligonucleotide microarray, which allowed a direct comparison of the forces between perfectly matched short oligonucleotides and those containing a single or double mismatch. Through this greatly increased sensitivity, the force contribution of a single AT base pair was derived. The results indicate that the contribution to forces from the stacking interactions is more important than that from hydrogen bonding.