Using Extraordinary Optical Transmission to Quantify Cardiac Biomarkers in Human Serum

For a biosensing platform to have clinical relevance in point-of-care (POC) settings, assay sensitivity, reproducibility, and ability to reliably monitor ...

National University of Singapore

At the nano-bio interface, human plasma differentially interacts with engineered nanomaterials through the creation of protein coronas, which in turn become primary determinants of both the pharmacokinetics and pharmacodynamics of circulating nanoparticles. Here, for the first time, the specific binding kinetics of the four major corona forming proteins (human serum albumin, fibrinogen, ApoA1, and polyclonal IgG) are determined for gold nanoparticles (AuNPs). Using a multiplexed surface plasmonic assay, highly reproducible measurements of on rate (k(on)), off rate (k(off)), and disassociation constant (K(D)), in addition to relative amounts of protein binding, are obtained. Dramatic differences in k(on) for individual components are shown as primary determinants of protein affinities, with k(on) ranging over nearly two orders of magnitude for the proteins studied, while k(off) remains within a factor of two for the set. The effect of polyethylene glycol (PEG) modification on plasma component binding is also studied and the effect of PEG length on human serum interaction is characterized through systematic screening of PEG molecular weight (2-30k). The effect of nanoparticle modification on particle targeting is also characterized through study of a hybrid AuNP system.

Component-Specific Analysis of Plasma Protein Corona Formation on Gold Nanoparticles Using Multiplexed Surface Plasmon Resonance.

Carbon nanotubes' (CNTs) hollow interior space has been explored for biomedical applications, such as drug repository against undesirable inactivation. To further devise CNTs as smart material for controlled release of cargo molecules, we propose the concept of "gold-carbon nanobottles". After encapsulating cis-diammineplatinum(II) dichloride (cisplatin, CDDP) in CNTs, we covalently attached gold nanoparticles (AuNPs) at the open-tips of CNTs via different cleavable linkages, namely hydrazine, ester, and disulfide-containing linkages. Compared with our previous study in which more than 80% of CDDP leaked from CNTs in 2 hours, AuNPs were found to significantly decrease such spontaneous release to <40%. In addition, CDDP release from AuNP-capped CNTs via disulfide linkage was selectively enhanced by twofolds in reducing conditions (namely with 1 mM dithiothreitol [DTT]), which mimic the intracellular environment. We treated human colon adenocarcinoma cells HCT116 with our CDDP-loaded gold-carbon nanobottles and examined the cell viability using lactate dehydrogenase assay. Interestingly, we found that our nanobottles with cleavable disulfide linkage exerted stronger cytotoxic effect in HCT116 compared with normal human fetal lung fibroblast cells IMR-90. Therefore, we infer that our nanobottles strategy with inbuilt disulfide linkage could attain selective release of payload in highly reductive tumor tissues while avoiding collateral damage to normal tissues.

In vitro controlled release of cisplatin from gold-carbon nanobottles via cleavable linkages.

The wetting behaviour of surfaces is believed to be affected by van der Waals (vdW) forces; however, there is no clear demonstration of this. With the isolation of two-dimensional vdW layered materials it is possible to test this hypothesis. In this paper, we report the wetting behaviour of vdW heterostructures which include chemical vapor deposition (CVD) grown graphene, molybdenum disulfide (MoS2) and tungsten disulfide (WS2) on few layers of hexagon boron nitride (h-BN) and SiO2/Si. Our study clearly shows that while this class of two-dimensional materials are not completely wetting transparent, there seems to be a significant amount of influence on their wetting properties by the underlying substrate due to dominant vdW forces. Contact angle measurements indicate that graphene and graphene-like layered transitional metal dichalcogenides invariably have intrinsically dispersive surfaces with a dominating London-vdW force-mediated wettability.

Surface energy and wettability of van der Waals structures.

In this manuscript, we demonstrate a method based on atomic force microscopy which enables local probing of surface wettability. The maximum pull-off force, obtained from force spectroscopy shows a remarkable correlation with the macroscopically observed water contact angle, measured over a wide variety of surfaces starting from hydrophilic, all the way through to hydrophobic ones. This relationship, consequently, facilitates the establishment of a universal behaviour. The adhesion forces scale with the polar component of surface energy. However, no such relation could be established with the dispersive component. Hence, we postulate that the force(s) which enable us to correlate the force spectroscopy data measured on the nanoscale to the macroscopic contact angle are primarily arising from electrostatic-dipole-dipole interactions at the solid-liquid interface. London forces play less of a role. This effect in is line with density functional theory (DFT) calculations suggesting a higher degree of hydroxylation of hydrophilic surfaces. This result shows that molecular simulations and measurements on an atomic scale can be extrapolated to macroscopic surface wetting problems.

Correlation of nanoscale behaviour of forces and macroscale surface wettability.

Strongly correlated electronic systems such as Transition Metal Oxides often possess various mid-gap states originating from intrinsic defects in these materials. In this paper, we investigate an extremely sharp Photoluminescence (PL) transition originating from such defect states in two widely used perovskites, LaAlO3 and SrTiO3. A detailed study of the PL as a function of temperature and magnetic field has been conducted to understand the behavior and origin of the transition involved. The temperature dependence of the PL peak position for SrTiO3 is observed to be opposite to that in LaAlO3. Our results reveal the presence of a spin/orbital character in these transitions which is evident from the splitting of these defect energy levels under a high magnetic field. These PL transitions have the potential for enabling non-contact thermal and field sensors.

Magneto-Optical Study of Defect Induced Sharp Photoluminescence in LaAlO3 and SrTiO3.

In this study we report the existence of novel ultraviolet (UV) and blue emission in rare-earth based perovskite NdGaO3 (NGO) and the systematic quench of the NGO photoluminescence (PL) by Ce doping. Study of room temperature PL was performed in both single-crystal and polycrystalline NGO (substrates and pellets) respectively. Several NGO pellets were prepared with varying Ce concentration and their room temperature PL was studied using 325 nm laser. It was found that the PL intensity shows a systematic quench with increasing Ce concentration. XPS measurements indicated that nearly 50% of Ce atoms are in the 4+ state. The PL quench was attributed to the novel concept of super hydrogenic dopant (SHD)", where each Ce4+ ion contributes an electron which forms a super hydrogenic atom with an enhanced Bohr radius, due to the large dielectric constant of the host. Based on the critical Ce concentration for complete quenching this SHD radius was estimated to be within a range of 0.85 nm and 1.15 nm whereas the predicted theoretical value of SHD radius for NdGaO3 is ~1.01 nm.

Origin and Quenching of Novel ultraviolet and blue emission in NdGaO3: Concept of Super-Hydrogenic Dopants.

Here, we report the presence of defect-related states with magnetic degrees of freedom in crystals of LaAlO3 and several other rare-earth based perovskite oxides using inelastic light scattering (Raman spectroscopy) at low temperatures in applied magnetic fields of up to 9 T. Some of these states are at about 140 meV above the valence band maximum while others are mid-gap states at about 2.3 eV. No magnetic impurity could be detected in LaAlO3 by Proton-Induced X-ray Emission Spectroscopy. We, therefore, attribute the angular momentum-like states in LaAlO3 to cationic/anionic vacancies or anti-site defects. Comparison with the other rare earth perovskites leads to the empirical rule that the magnetic-field-sensitive transitions require planes of heavy elements (e.g. lanthanum) and oxygen without any other light cations in the same plane. These magnetic degrees of freedom in rare earth perovskites with useful dielectric properties may be tunable by appropriate defect engineering for magneto-optic applications.

Magnetic Modes in Rare Earth Perovskites: A Magnetic-Field-Dependent Inelastic Light Scattering study.

Non-volatile memories will play a decisive role in the next generation of digital technology. Flash memories are currently the key player in the field, yet they fail to meet the commercial demands of scalability and endurance. Resistive memory devices, and in particular memories based on low-cost, solution-processable and chemically tunable organic materials, are promising alternatives explored by the industry. However, to date, they have been lacking the performance and mechanistic understanding required for commercial translation. Here we report a resistive memory device based on a spin-coated active layer of a transition-metal complex, which shows high reproducibility (∼350 devices), fast switching (≤30 ns), excellent endurance (∼1012 cycles), stability (>106 s) and scalability (down to ∼60 nm2). In situ Raman and ultraviolet-visible spectroscopy alongside spectroelectrochemistry and quantum chemical calculations demonstrate that the redox state of the ligands determines the switching states of the device whereas the counterions control the hysteresis. This insight may accelerate the technological deployment of organic resistive memories.

Abhijeet Patra

NUS Nanoscience and Nanotechnology Initiative

National University of Singapore

Using Extraordinary Optical Transmission to Quantify Cardiac Biomarkers in Human Serum

Abhijeet Patra

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National University of Singapore

Using Extraordinary Optical Transmission to Quantify Cardiac Biomarkers in Human Serum

NUS Nanoscience and Nanotechnology Initiative