Flexible Narrowband Ultraviolet Photodetectors with Photomultiplication Based on Wide Band Gap Conjugated Polymer and Inorganic Nanoparticles

Lightweight and flexible ultraviolet (UV) photodetectors (PDs) have wide applications and have attracted more attention. PDs using organic and inorganic nanocomposites as active layers with a photodiode configuration could achieve photomultiplication and narrowband photoresponse via the control of microstructure and thickness of active layers. Here, we fabricated flexible UV PDs on indium tin oxide-coated poly­(ethylene terephthalate) substrates with a nanocomposite active layer composed of ZnO nanoparticles blended with a wide band gap conjugated polymer, poly­[(9,9-dioctylfluorenyl-2,7-diyl)-<i>alt</i>-<i>co</i>-(bithiophene)] (F8T2). As a result of the wavelength-dependent penetration depth of light in the active layer, the fabricated flexible UV PDs showed two narrow response peaks at 360 and 510 nm under reverse biases in the external quantum efficiency (EQE) spectra with full width at half maximum (FWHM) less than 20 nm. Both responses exhibited greater than 100% EQE, indicating a photomultiplication effect, whereas the UV response at 360 nm was 10 times stronger under −15 V bias. The fabricated flexible UV PDs were bent under both tensile and compressive stress to a curvature of 2.1 cm^–1, each with 50 repetitions. The peak specific detectivity (<i>D</i>*) only decreased by about 5% in total, the FWHM was well retained below 20 nm and the response speed remained almost constant after two types of bending, demonstrating mechanical flexibility and photoresponse stability of the fabricated flexible UV PDs. The photodiode configuration with nanocomposite active layers offers a promising route to make flexible and conformable narrowband, photomultiplication-type photodetectors for modern applications

Directly Functionalizable Surface Platform for Protein Arrays in Undiluted Human Blood Plasma

Protein arrays are a high-throughput approach for proteomic profiling, vital for achieving a greater understanding of biological systems, in addition to disease diagnostics and monitoring therapeutic treatments. In this work, zwitterionic carboxybetaine polymer (pCB) coated substrates were investigated as an array surface platform to enable convenient amino-coupling chemistry on a single directly functionalizable and unblocked film for the sensitive detection of target analytes from undiluted human blood plasma. Using a surface plasmon resonance (SPR) imaging sensor, the antibody immobilization conditions which provided excellent spot morphology and the largest antigen response were determined. It was found that pCB functionalization and the corresponding antigen detection both increased with pH and antibody concentration. Additionally, immobilization only required an aqueous buffer without the need for additives to improve spot quality. The nonspecific protein adsorption to undiluted human plasma on both the antibody immobilized pCB spots and the background were found to be about 9 and 6 ng/cm², respectively. A subsequent array consisting of three antibodies spotted onto pCB revealed little cross-reactivity for antigens spiked into the undiluted plasma. The low postfunctionalized nonfouling properties combined with antibody amplification showed similar sensitivities achievable with conventional spectroscopic SPR sensors and the same pCB films, but now with high-throughput capabilities. This represents the first demonstration of low fouling properties following antibody functionalization on protein arrays from undiluted human plasma and indicates the great potential of the pCB platform for high-throughput protein analysis

Surface-Enhanced Raman Scattering on Gold Nanohole Arrays in Symmetrical Dielectric Environments Exhibiting Electric Field Extension

The electromagnetic enhancement in surface-enhanced Raman scattering (SERS) caused by localized surface plasmon resonance is a near-field effect, often limiting the practicality of SERS in many applications. However, no attempts have been made to investigate field extension through symmetrical refractive index modulation in a SERS-based system. Here, we report the development and characterization of refractive index-matched SERS substrates supporting electric field extension to realize what is termed “long-range SERS” (LR-SERS). Finite-difference time-domain simulations were employed to tune the plasmonic responses and investigate electric field distributions of gold nanohole arrays (NHAs) as a function of the dielectric environment and geometric parameters. SERS substrates supporting long-range behavior were compared against “conventional” substrates without long-range behavior. SERS intensities from rhodamine 6G (R6G) aqueous solutions of 2.0 × 10³ and 1.5 × 10² counts s^–1 mW^–1 were produced by the LR-SERS and conventional substrates, respectively, on the gold surface. Moreover, a signal response of 9.0 × 10¹ counts s^–1 mW^–1 was produced by LR-SERS substrates with a 10 nm separation between the R6G solution and NHA, while no signal was observed from the conventional substrate. As a proof of principle study, the results demonstrate the potential to use LR-SERS substrates in applications where the target analyte is located further from the SERS-active surface

Two-Layer Architecture Using Atom Transfer Radical Polymerization for Enhanced Sensing and Detection in Complex Media

A novel, two-layer hierarchical architecture based on surface-initiated atom transfer radical polymerization was investigated. It combines a thin and highly dense first layer, for nonfouling properties, with a loose second layer for high immobilization levels of active biomolecules. Sodium azide treatment, to reduce the concentration of macroinitiators on the first layer for reinitiation, and by controlling the polydispersity allowed one to achieve three polymer architectures with low, moderate, or high azide substitution. Moderate substitution enabled the highest immobilization levels with a nonfouling background. Integration with dual-functional zwitterionic poly­(carboxybetaine) made this platform suitable for applications in undiluted complex media such as blood. It was demonstrated via a surface plasmon resonance biosensor that antigen accessibility and antibody loading were greatly improved. These results indicate the two-layer strategy as a generic concept suitable for applications from diagnostics to medical coatings in order to maximize and minimize specific and nonspecific responses, respectively

Dry Film Refractive Index as an Important Parameter for Ultra-Low Fouling Surface Coatings

Here we demonstrate that the film refractive index (RI) can be an even more important parameter than film thickness for identifying nonfouling polymer films to undiluted human blood plasma and serum. The film thickness and RI are two parameters obtained from ellipsometry. Previously, film thickness has been correlated to ultra-low fouling properties. Practically, the film RI can be used to characterize polymer density but is often overlooked. By varying the water content in the surface-initiated atom transfer radical polymerization of zwitterionic carboxybetaine, a minimum of ∼1.5 RI units was necessary to achieve <5 ng/cm² of adsorption from undiluted human serum. A model of the film structure versus water content was also developed. These results point to an important parameter and simple approach for identifying surface coatings suitable for real-world applications involving complex media. Therefore, ultra-low fouling using a thin film is possible if it is densely packed

A Robust Graft-to Strategy To Form Multifunctional and Stealth Zwitterionic Polymer-Coated Mesoporous Silica Nanoparticles

Mesoporous silica nanoparticles (MSNs) are a new class of carrier materials promising for drug/gene delivery and many other important applications. Stealth coatings are necessary to maintain their stability in complex media. Herein, a biomimetic polymer conjugate containing one ultralow fouling poly­(carboxybetaine) (pCBMA) chain and one surface-adhesive catechol (DOPA) residue group was efficiently grafted to the outer surface of SBA-15 type MSNs using a convenient and robust method. The cytotoxicity of SBA-15-DOPA-pCBMAs was evaluated by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Results showed no significant decrease in cell viability at the tested concentration range. Macrophage cell uptake studies revealed that the uptake ratios of SBA-15-DOPA-pCBMAs were much lower than that of parent MSNs. Furthermore, inductively coupled plasma mass spectrometry (ICP-MS) analysis results showed that after SBA-15-DOPA-pCBMAs were conjugated with a targeting cyclo-[Arg-Gly-Asp-d-Tyr-Lys] (cRGD) peptide, uptake by bovine aortic endothelial cells (BAECs) was notably increased. Results indicated that cRGD-functionalized MSNs were able to selectively interact with cells expressing αvβ3 integrin. Thus, MSNs with DOPA-pCBMAs are promising as stealth multifunctional biocarriers for targeted drug delivery or diagnostics

Stealth Surface Modification of Surface-Enhanced Raman Scattering Substrates for Sensitive and Accurate Detection in Protein Solutions

Reliable surface-enhanced Raman scattering (SERS) based biosensing in complex media is impeded by nonspecific protein adsorptions. Because of the near-field effect of SERS, it is challenging to modify SERS-active substrates using conventional nonfouling materials without introducing interference from their SERS signals. Herein, we report a stealth surface modification strategy for sensitive, specific and accurate detection of fructose in protein solutions using SERS by forming a mixed self-assembled monolayer (SAM). The SAM consists of a short zwitterionic thiol, <i>N</i>,<i>N</i>-dimethyl-cysteamine-carboxybetaine (CBT), and a fructose probe 4-mercaptophenylboronic acid (4-MPBA). The specifically designed and synthesized CBT not only resists protein fouling effectively, but also has very weak Raman activity compared to 4-MPBA. Thus, the CBT SAM provides a stealth surface modification to SERS-active substrates. The surface compositions of mixed SAMs were investigated using X-ray photoelectron spectroscopy (XPS) and SERS, and their nonfouling properties were studied with a surface plasmon resonance (SPR) biosensor. The mixed SAM with a surface composition of 94% CBT demonstrated a very low bovine serum albumin (BSA) adsorption (∼3 ng/cm²), and moreover, only the 4-MPBA signal appeared in the SERS spectrum. With the use of this surface-modified SERS-active substrate, quantification of fructose over clinically relevant concentrations (0.01–1 mM) was achieved. Partial least-squares regression (PLS) analysis showed that the detection sensitivity and accuracy were maintained for the measurements in 1 mg/mL BSA solutions. This stealth surface modification strategy provides a novel route to introduce nonfouling property to SERS-active substrates for SERS biosensing in complex media

Sensitive and Fast Detection of Fructose in Complex Media via Symmetry Breaking and Signal Amplification Using Surface-Enhanced Raman Spectroscopy

A new strategy is proposed to sensitively and rapidly detect analytes with weak Raman signals in complex media using surface-enhanced Raman spectroscopy (SERS) via detecting the SERS signal changes of the immobilized probe molecules on SERS-active substrates upon binding of the analytes. In this work, 4-mercaptophenylboronic acid (4-MPBA) was selected as the probe molecule which was immobilized on the gold surface of a quasi-three-dimensional plasmonic nanostructure array (Q3D-PNA) SERS substrate to detect fructose. The molecule of 4-MPBA possesses three key functions: molecule recognition and reversible binding of the analyte via the boronic acid group, amplification of SERS signals by the phenyl group and thus shielding of the background noise of complex media, and immobilization on the surface of SERS-active substrates via the thiol group. Most importantly, the symmetry breaking of the 4-MPBA molecule upon fructose binding leads to the change of area ratio between totally symmetric 8a ring mode and nontotally symmetric 8b ring mode, which enables the detection. The detection curves were obtained in phosphate-buffered saline (PBS) and in undiluted artificial urine at clinically relevant concentrations, and the limit of detection of 0.05 mM was achieved

Cellulose Paper Sensors Modified with Zwitterionic Poly(carboxybetaine) for Sensing and Detection in Complex Media

Poly­(carboxybetaine) (PCB) functionalized cellulose paper was used as a paper-based microfluidic device. The results showed that the PCB modified paper sensor was able to achieve (a) more rapid and sensitive glucose detection from undiluted human serum compared to bare cellulose and (b) specific antigen detection via covalently immobilized antibodies

Simple Physical Approach to Reducing Frictional and Adhesive Forces on a TiO₂ Surface via Creating Heterogeneous Nanopores

A simple physical strategy to reduce the frictional and adhesive forces on TiO₂ films was proposed by constructing mesoporous TiO₂ films with heterogeneously distributed nanopores on the film surfaces. In comparison, TiO₂ films with densely packed nanoparticles were also prepared. The crystal structure and morphology of the films were characterized with Raman spectroscopy, field emission scanning electron microscopy (FESEM), and atomic force microscopy (AFM). It was found that the TiO₂(B) phase exists in the mesoporuos TiO₂ films but not in the densely packed films. The existence of TiO₂(B) plays a significant role in creating and maintaining the nanopores in the mesoporous TiO₂ films. The frictional and adhesive forces were measured on both films using AFM. The mesoporous films exhibit two typical adhesion forces of around 3 and 12 nN in the force distribution profile whereas the densely packed films show only one around 12 nN. The frictional coefficients were 2.6 × 10^–3 and 6.7 × 10^–2 for the mesoporous and densely packed TiO₂ films, respectively. A model based on the atomic structures of a thin film of water molecules adsorbed on TiO₂ surfaces leading to hydrophobic effects was proposed to understand the lower frictional and adhesive forces observed on the mesoporous TiO₂ films. This simple physical approach to reducing the frictional and adhesive forces on TiO₂ films could have broad applications to a variety of surface coatings