Ultrahigh Capacitive Energy Density in Stratified 2D Nanofiller-Based Polymer Dielectric Films.

Dielectric capacitors are critical components in electronics and energy storage devices. The polymer-based dielectric capacitors have the advantages of device flexibility, fast charge-discharge rates, low loss, and graceful failure. Elevating the use of polymeric dielectric capacitors for advanced energy applications such as electric vehicles (EVs), however, requires significant enhancement of their energy densities. Here, we report a polymer thin film heterostructure-based capacitor of poly(vinylidene fluoride)/poly(methyl methacrylate) with stratified 2D nanofillers (Mica or h-BN nanosheets) (PVDF/PMMA-2D fillers/PVDF), that shows enhanced permittivity, high dielectric strength, and an ultrahigh energy density of ≈75 J/cm3 with efficiency over 79%. Density functional theory calculations verify the observed permittivity enhancement. This approach of using oriented 2D nanofillers-based polymer heterostructure composites is expected to be versatile for designing high energy density thin film polymeric dielectric capacitors for myriads of applications.

Comparative Study of Polymer-Grafted BaTiO3 Nanoparticles Synthesized Using Normal ATRP as Well as ATRP and ARGET-ATRP with Sacrificial Initiator with a Focus on Controlling the Polymer Graft Density and Molecular Weight.

Structurally well-defined polymer-grafted nanoparticle hybrids are highly sought after for a variety of applications, such as antifouling, mechanical reinforcement, separations, and sensing. Herein, we report the synthesis of poly(methyl methacrylate) grafted- and poly(styrene) grafted-BaTiO3 nanoparticles using activator regeneration via electron transfer (ARGET ATRP) with a sacrificial initiator, atom transfer radical polymerization (normal ATRP), and ATRP with sacrificial initiator, to understand the role of the polymerization procedure in influencing the structure of nanoparticle hybrids. Irrespective of the polymerization procedure adopted for the synthesis of nanoparticle hybrids, we noticed PS grafted on the nanoparticles showed moderation in molecular weight and graft density (ranging from 30,400 to 83,900 g/mol and 0.122 to 0.067 chain/nm2) compared to PMMA-grafted nanoparticles (ranging from 44,620 to 230,000 g/mol and 0.071 to 0.015 chain/nm2). Reducing the polymerization time during ATRP has a significant impact on the molecular weight of polymer brushes grafted on the nanoparticles. PMMA-grafted nanoparticles synthesized using ATRP had lower graft density and considerably higher molecular weight compared to PS-grafted nanoparticles. However, the addition of a sacrificial initiator during ATRP resulted in moderation of the molecular weight and graft density of PMMA-grafted nanoparticles. The use of a sacrificial initiator along with ARGET offered the best control in achieving lower molecular weight and narrow dispersity for both PS (37,870 g/mol and PDI of 1.259) and PMMA (44,620 g/mol and PDI of 1.263) nanoparticle hybrid systems.

Polymer-Grafted Nanoparticles with Variable Grafting Densities for High Energy Density Polymeric Nanocomposite Dielectric Capacitors.

Designing high energy density dielectric capacitors for advanced energy storage systems needs nanocomposite-based dielectric materials, which can utilize the properties of both inorganic and polymeric materials. Polymer-grafted nanoparticle (PGNP)-based nanocomposites alleviate the problems of poor nanocomposite properties by providing synergistic control over nanoparticle and polymer properties. Here, we synthesize "core-shell" barium titanate-poly(methyl methacrylate) (BaTiO3-PMMA) grafted PGNPs using surface-initiated atom transfer polymerization (SI-ATRP) with variable grafting densities of (0.303 to 0.929) chains/nm2 and high molecular masses (97700 g/mL to 130000 g/mol) and observe that low grafted density and high molecular mass based PGNP show high permittivity, high dielectric strength, and hence higher energy densities (≈ 5.2 J/cm3) as compared to the higher grafted density PGNPs, presumably due to their "star-polymer"-like conformations with higher chain-end densities that are known to enhance breakdown. Nonetheless, these energy densities are an order of magnitude higher than their nanocomposite blend counterparts. We expect that these PGNPs can be readily used as commercial dielectric capacitors, and these findings can serve as guiding principles for developing tunable high energy density energy storage devices using PGNP systems.

Enhanced Dielectric Strength and Capacitive Energy Density of Cyclic Polystyrene Films.

The maximum capacitive energy stored in polymeric dielectric capacitors, which are ubiquitous in high-power-density devices, is dictated by the dielectric breakdown strength of the dielectric polymer. The fundamental mechanisms of the dielectric breakdown, however, remain unclear. Based on a simple free-volume model of the polymer fluid state, we hypothesized that the free ends of linear polymer chains might act as "defect" sites, at which the dielectric breakdown can initiate. Thus, the dielectric breakdown strength of cyclic polymers should exhibit enhanced stability in comparison to that of their linear counterparts having the same composition and similar molar mass. This hypothesis is supported by the ∼50% enhancement in the dielectric breakdown strength and ∼80% enhancement in capacitive energy density of cyclic polystyrene melt films in comparison to corresponding linear polystyrene control films. Furthermore, we observed that cyclic polymers exhibit a denser packing density than the linear chain melts, an effect that is consistent with and could account for the observed property changes. Our work demonstrates that polymer topology can significantly influence the capacitive properties of polymer films, and correspondingly, we can expect polymer topology to influence the gas permeability, shear modulus, and other properties of thin films dependent on film density.

Correction to "An Investigation of the Interaction Between Bovine Serum Albumin-Conjugated Silver Nanoparticles and the Hydrogel in Hydrogel Nanocomposites".

[This corrects the article DOI: 10.1021/acsomega.1c00834.].

Recent Advances in the Synthesis of Polymer-Grafted Low-K and High-K Nanoparticles for Dielectric and Electronic Applications.

The synthesis of polymer-grafted nanoparticles (PGNPs) or hairy nanoparticles (HNPs) by tethering of polymer chains to the surface of nanoparticles is an important technique to obtain nanostructured hybrid materials that have been widely used in the formulation of advanced polymer nanocomposites. Ceramic-based polymer nanocomposites integrate key attributes of polymer and ceramic nanomaterial to improve the dielectric properties such as breakdown strength, energy density and dielectric loss. This review describes the "grafting from" and "grafting to" approaches commonly adopted to graft polymer chains on NPs pertaining to nano-dielectrics. The article also covers various surface initiated controlled radical polymerization techniques, along with templated approaches for grafting of polymer chains onto SiO2, TiO2, BaTiO3, and Al2O3 nanomaterials. As a look towards applications, an outlook on high-performance polymer nanocomposite capacitors for the design of high energy density pulsed power thin-film capacitors is also presented.

An Investigation of the Interaction between Bovine Serum Albumin-Conjugated Silver Nanoparticles and the Hydrogel in Hydrogel Nanocomposites.

Nanocomposite hydrogels are attracting significant interest due to their potential use in drug delivery systems and tissue scaffolds. Stimuli-responsive hydrogel nanocomposites are of particular interest due to sustained release of therapeutic agents from the hydrogel. However, challenges such as controlled release of therapeutic agents exist because of limited understanding of the interactions between the therapeutic agent and the hydrogel. To investigate the interaction, we synthesize a hydrogel nanocomposite by crosslinking the hydrogel precursors (tetrazine-modified polyethylene glycol and norbornene-modified hyaluronic acid) using click chemistry while bovine serum albumin-capped silver nanoparticles were encapsulated in situ in the matrix. The interaction between the nanoparticles and the hydrogel was studied by a combination of spectroscopic techniques. X-ray photoelectron spectroscopy results suggest that the hydrogel molecule rearranges so that polyethylene glycol is pointing up toward the surface while hyaluronic acid folds to interact with bovine serum albumin of the nanoparticles. Hyaluronic acid, facing inward, may interact with the nanoparticle via hydrogen bonding. The hydrogel nanocomposite showed antibacterial activity against Gram-positive/Gram-negative bactericides, supporting time-based nanoparticle release results. Our findings about interactions between the nanoparticles and the hydrogel can be useful in the formulation of next generation of hydrogel nanocomposites.

Recent developments in the synthesis of chemically modified nanomaterials for use in dielectric and electronics applications.

Polymer nanocomposites (PNC) have attracted enormous scientific and technological interest due to their applications in energy storage, electronics, biosensing, drug delivery, cosmetics and packaging industry. Nanomaterials (platelet, fibers, spheroids, whiskers, rods) dispersed in different types of polymer matrices constitute such PNC. The degree of dispersion of the inorganic nanomaterials in the polymer matrix, as well as the structured arrangement of the nanomaterials, are some of the key factors influencing the overall performance of the nanocomposite. To this end, the surface functionalization of the nanomaterials determines its state of dispersion within the polymer matrix. For energy storage and electronics, these nanomaterials are usually chosen for their dielectric properties for enhancing the performance of device applications. Although several reviews on surface modification of nanomaterials have been reported, a review on the surface functionalization of nanomaterials as it pertains to polymer dielectrics is currently lacking. This review summarizes the recent developments in the surface modification of important metal oxide dielectric nanomaterials including Silicon dioxide (SiO2), titanium dioxide (TiO2), barium titanate (BaTiO3), and aluminum oxide (Al2O3) by chemical agents such as silanes, phosphonic acids, and dopamine. We report the impact of chemical modification of the nanomaterial on the dielectric performance (dielectric constant, breakdown strength, and energy density) of the nanocomposite. Aside from bringing novice and experts up to speed in the area of polymer dielectric nanocomposites, this review will serve as an intellectual resource in the selection of appropriate chemical agents for functionalizing nanomaterials for use in specific polymer matrix so as to potentially tune the final performance of nanocomposite.

High broadband photoconductivity of few-layered MoS2 field-effect transistors measured using multi-terminal methods: effects of contact resistance.

Among the layered two dimensional semiconductors, molybdenum disulfide (MoS2) is considered to be an excellent candidate for applications in optoelectronics and integrated circuits due to its layer-dependent tunable bandgap in the visible region, high ON/OFF current ratio in field-effect transistors (FET) and strong light-matter interaction properties. In this study, using multi-terminal measurements, we report high broadband photocurrent response (R) and external quantum efficiency (EQE) of few-atomic layered MoS2 phototransistors fabricated on a SiO2 dielectric substrate and encapsulated with a thin transparent polymer film of Cytop. The photocurrent response was measured using a white light source as well as a monochromatic light of wavelength λ = 400 nm-900 nm. We measured responsivity using a 2-terminal configuration as high as R = 1 × 103 A W-1 under white light illumination with an optical power Popt = 0.02 nW. The R value increased to 3.5 × 103 A W-1 when measured using a 4-terminal configuration. Using monochromatic light on the same device, the measured values of R were 103 and 6 × 103 A W-1 under illumination of λ = 400 nm when measured using 2- and 4-terminal methods, respectively. The highest EQE values obtained using λ = 400 nm were 105% and 106% measured using 2- and 4-terminal configurations, respectively. The wavelength dependent responsivity decreased from 400 nm to the near-IR region at 900 nm. The observed photoresponse, photocurrent-dark current ratio (PDCR), detectivity as a function of applied gate voltage, optical power, contact resistances and wavelength were measured and are discussed in detail. The observed responsivity is also thoroughly studied as a function of contact resistance of the device.

Tuning the Relaxation of Nanopatterned Polymer Films with Polymer-Grafted Nanoparticles: Observation of Entropy-Enthalpy Compensation.

Polymer films provide a versatile platform in which complex functional relief patterns can be thermally imprinted with a resolution down to few nanometers. However, a practical limitation of this method is the tendency for the imprinted patterns to relax ("slump"), leading to loss of pattern fidelity over time. While increasing temperature above glass transition temperature ( Tg) accelerates the slumping kinetics of neat films, we find that the addition of polymer-grafted nanoparticles (PGNP) can greatly enhance the thermal stability of these patterns. Specifically, increasing the concentration of poly(methyl methacrylate) (PMMA) grafted titanium dioxide (TiO2) nanoparticles in the composite films slows down film relaxation dynamics, leading to enhanced pattern stability for the temperature range that we investigated. Interestingly, slumping relaxation time is found to obey an entropy-enthalpy compensation (EEC) relationship with varying PGNP concentration, similar to recently observed relaxation of strain-induced wrinkling in glassy polymer films having variable film thickness. The compensation temperature,  Tcomp was found to be in the vicintity of the bulk  Tg of PMMA. Our results suggest a common origin of EEC relaxation in patterned polymer thin films and  nanocomposites.

Confined Pattern-Directed Assembly of Polymer-Grafted Nanoparticles in a Phase Separating Blend with a Homopolymer Matrix.

The controlled organization of nanoparticle (NP) constituents into superstructures of well-defined shape, composition and connectivity represents a continuing challenge in the development of novel hybrid materials for many technological applications. We show that the phase separation of polymer-tethered nanoparticles immersed in a chemically different polymer matrix provides an effective and scalable method for fabricating defined submicron-sized amorphous NP domains in melt polymer thin films. We investigate this phenomenon with a view towards understanding and controlling the phase separation process through directed nanoparticle assembly. In particular, we consider isothermally annealed thin films of polystyrene-grafted gold nanoparticles (AuPS) dispersed in a poly(methyl methacrylate) (PMMA) matrix. Classic binary polymer blend phase separation related morphology transitions, from discrete AuPS domains to bicontinuous to inverse domain structure with increasing nanoparticle composition is observed, yet the kinetics of the AuPS/PMMA polymer blends system exhibit unique features compared to the parent PS/PMMA homopolymer blend. We further illustrate how to pattern-align the phase-separated AuPS nanoparticle domain shape, size and location through the imposition of a simple and novel external symmetry-breaking perturbation via soft-lithography. Specifically, submicron-sized topographically patterned elastomer confinement is introduced to direct the nanoparticles into kinetically controlled long-range ordered domains, having a dense yet well-dispersed distribution of non-crystallizing nanoparticles. The simplicity, versatility and roll-to-roll adaptability of this novel method for controlled nanoparticle assembly should make it useful in creating desirable patterned nanoparticle domains for a variety of functional materials and applications.

Directed Self-Assembly of Block Copolymers for High Breakdown Strength Polymer Film Capacitors.

Emerging needs for fast charge/discharge yet high-power, lightweight, and flexible electronics requires the use of polymer-film-based solid-state capacitors with high energy densities. Fast charge/discharge rates of film capacitors on the order of microseconds are not achievable with slower charging conventional batteries, supercapacitors and related hybrid technologies. However, the current energy densities of polymer film capacitors fall short of rising demand, and could be significantly enhanced by increasing the breakdown strength (EBD) and dielectric permittivity (εr) of the polymer films. Co-extruded two-homopolymer component multilayered films have demonstrated much promise in this regard showing higher EBD over that of component polymers. Multilayered films can also help incorporate functional features besides energy storage, such as enhanced optical, mechanical, thermal and barrier properties. In this work, we report accomplishing multilayer, multicomponent block copolymer dielectric films (BCDF) with soft-shear driven highly oriented self-assembled lamellar diblock copolymers (BCP) as a novel application of this important class of self-assembling materials. Results of a model PS-b-PMMA system show ∼50% enhancement in EBD of self-assembled multilayer lamellar BCP films compared to unordered as-cast films, indicating that the breakdown is highly sensitive to the nanostructure of the BCP. The enhancement in EBD is attributed to the "barrier effect", where the multiple interfaces between the lamellae block components act as barriers to the dielectric breakdown through the film. The increase in EBD corresponds to more than doubling the energy storage capacity using a straightforward directed self-assembly strategy. This approach opens a new nanomaterial paradigm for designing high energy density dielectric materials.

Antimicrobial and cell viability measurement of bovine serum albumin capped silver nanoparticles (Ag/BSA) loaded collagen immobilized poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) film.

Bacterial infection of orthopedic devices has been a major concern in joint replacement procedures. Therefore, this study is aimed at formulating collagen immobilized poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) film loaded with bovine serum albumin capped silver nanoparticles (Ag/BSA NPs) to inhibit bacterial growth while retaining/promoting osteoblast cells viability. The nanoparticles loaded collagen immobilized PHBV film was characterized for its composition by X-ray Photoelectron Spectroscopy and Anodic Stripping Voltammetry. The extent of loading of Ag/BSA NPs on collagen immobilized PHBV film was found to depend on the chemistry of the functionalized PHBV film and the concentration of Ag/BSA NPs solution used for loading nanoparticles. Our results showed that more Ag/BSA NPs were loaded on higher molecular weight collagen immobilized PHEMA-g-PHBV film. Maximum loading of Ag/BSA NPs on collagen immobilized PHBV film was observed when 16ppm solution was used for adsorption studies. Colony forming unit and optical density measurements showed broad antimicrobial activity towards Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa at significantly lower concentration i.e., 0.19 and 0.31µg/disc, compared to gentamicin and sulfamethoxazole trimethoprim while MTT assay showed that released nanoparticles from Ag/BSA NPs loaded collagen immobilized PHBV film has no impact on MCTC3-E1 cells viability.

Dispersion morphology and correlation to moduli using buckling metrology in clay-biopolymer nanocomposite thin films.

Structure-interaction-mechanical property correlation in bionanocomposite thin films is an area of growing interest for research and application areas from barrier to molecular transport to UV blocking layers for polymer solar cells to dielectric properties modification. Here we study flow coated ultrathin to thin films (70-150 nm) of clay bionanocomposites to understand the nanoparticle dispersion and its effect on nanomechanical properties. Binary and ternary thin film systems of polylactide (PLA), polycaprolactone (PCL), and Cloisite 30B (C30B) clay platelets were investigated. While C30B was only partially intercalated by PLA, it was almost completely intercalated by PCL due to strong hydrogen bonding. In addition, the dispersion of C30B improved continuously and linearly with increasing PCL content in homogeneously cast blended PLA:PCL. GIWAXS confirmed that the intercalated clay platelets in PLA and PCL were dominantly oriented parallel to the substrate. The method of strain induced elastic buckling instability for mechanical measurements (SIEBIMM) showed that pure PLA and PCL had in-plane modulus unchanged from bulk values for this range of ultrathin-thin films. In PLA/C30B nanocomposite thin films, the in-plane elastic modulus rapidly increased by up to 26% with 2 wt % C30B, but saturated thereafter up to 10 wt % C30B forming C30B aggregates. On the other hand, the in-plane elastic modulus of PCL/C30B thin films increased linearly by up to 43% with 10 wt % C30B due to the higher interaction driven dispersion, results that were shown to fit well with the Halpin-Tsai model. We conclude that the different strengthening behavior came from different interaction driven dispersion states of C30B in polymer matrices, governed by their molecular structures.

Synthesis and characterization of collagen grafted poly(hydroxybutyrate-valerate) (PHBV) scaffold for loading of bovine serum albumin capped silver (Ag/BSA) nanoparticles in the potential use of tissue engineering application.

The objective of this study is to synthesize and characterize collagen grafted poly(3-hydroxylbutyrate-co-3-hydroxylvalerate) (PHBV) film for loading of BSA capped silver (Ag/BSA) nanoparticles. Thermal radical copolymerization and aminolysis methods were used to functionalize macroporous PHBV, followed by collagen grafting so as to formulate collagen-g-poly(hydroxyethylmethyl acrylate)-g-poly(3-hydroxylbutyrate-co-3-hydroxylvalerate) [collagen-g-PHEMA-g-PHBV] and collagen-g-aminated-poly(3-hydroxylbutyrate-co-3-hydroxylvalerate) [collagen-g-NH2-PHBV] films, respectively. Spectroscopic (FTIR, XPS), physical (SEM), and thermal (TGA) techniques were used to characterize the functionalized PHBV films. The amount of collagen present on grafted PHBV film was quantified by the Bradford method. The Ag/BSA nanoparticles were then loaded on collagen grafted and untreated PHBV films, and the nanoparticles loading were determined by atomic absorption spectrometry. The amount of nanoparticles loaded on collagen grafted PHBV film was found to be significantly greater than that on the untreated PHBV film. The nanoparticles loaded PHBV film can potentially serve as a scaffold to promote the growth of bone cells while inhibiting the bacterial growth.

SPR studies of the adsorption of silver/bovine serum albumin nanoparticles (Ag/BSA NPs) onto the model biological substrates.

The primary objective of this study is to investigate the interactive forces that promote the adsorption of bio-conjugated nanoparticles onto proteins. To elucidate the interactive forces, we demonstrate an approach using synthetic and model biological surfaces to study adsorption of bio-conjugated nanoparticles. Real-time adsorption of BSA conjugated silver nanoparticles (Ag/BSA NPs) on the immobilized substrates was followed by surface plasmon resonance (SPR). The extent of adsorption of the nanoparticles on the synthetic surface was found to be larger for self-assembled monolayers (SAMs) with ionizable terminal groups and lower for SAMs with unionizable terminal groups. For model biological substrate, the extent of nanoparticles adsorption was found to relate to the pKa of immobilized proteins. For collagen immobilized substrate, the adsorption of Ag/BSA nanoparticles showed a significantly higher SPR response than that of free BSA. The extent of nanoparticles adsorption on the collagen immobilized substrate was also influenced by the type and concentration of electrolyte used in dispersing nanoparticles. Our findings indicate that the adsorption of nanoparticles to immobilized surface has contributions from electrostatic interactions, hydrophobic, and/or hydrogen bonding. This work provides the framework to study interactions that may arise when bio-conjugated nanoparticles are transported in biological systems.

Adsorption-desorption study of BSA conjugated silver nanoparticles (Ag/BSA NPs) on collagen immobilized substrates.

There has been a growing interest in the use of protein conjugated nanoparticles for applications in biomedical, sensing, and advanced imaging. The objective of this study was to understand the interaction of protein conjugated silver nanoparticles (Ag/BSA NPs) with biological substrate (collagen layer). The adsorption behavior of synthesized Ag/BSA NPs on collagen immobilized silanized surface was followed by UV-vis spectroscopy by initially studying the formation of collagen layer and subsequent adsorption of Ag/BSA NPs to the immobilized layer. Surface plasmon resonance (SPR) data provided the real time profile of adsorption of Ag/BSA NPs from solution onto collagen immobilized and control substrates as well as desorption of nanoparticles from the substrates. The retention of NPs to substrate is sensitive to chemistry of the underlying substrate and on the external environment. UV-vis and atomic absorption spectrometric analysis of Ag/BSA NPs desorption performed under different pH conditions showed more NPs retained at physiological pH than the acidic and basic conditions. Nanoparticles retention on collagen immobilized substrate at physiological pH could influence properties of biological interest such as circulation lifetime and biodistribution of nanoparticles in the body.

Characterization of non-equilibrium nanoparticle adsorption on a model biological substrate.

The kinetics of nanoparticle (NP) adsorption on a model biological interface (collagen) is measured in microfluidic channels using surface plasmon resonance (SPR) imaging over a range of CdSe/ZnS quantum dot concentrations to investigate the underlying binding process. Spherical CdSe/ZnS core-shell NP, derivatized with 3-mercaptopropionic acid (3-MPA), were considered to be model NPs because of their widespread use in biological applications and their relatively monodisperse size. The kinetic adsorption data suggests that the binding between the NP and the collagen substrate is irreversible at room temperature (pH approximately 7.4), and this type of adsorption process was further characterized in the context of a surface absorption model. Specifically, diffusion-limited adsorption was found to predominate the adsorption process at lower concentrations (<0.4 micromol/L), and NP adsorption was reaction-limited at higher concentration (>0.4 micromol/L). A limited pH study of our system indicates that NPs desorb from collagen under acidic conditions (pH 5.5); no significant desorption was observed under neutral and basic pH conditions. These observations are consistent with electrostatic interactions being the dominant force governing NP desorption from collagen substrates. Our present methodology for characterizing the seemingly irreversible NP adsorption complements our earlier study where NP adsorption onto weakly adsorbing surfaces (self-assembled monolayers) was characterized by Langmuir NP adsorption measurements.

Biological response of osteoblast-like UMR-106 cells to the modified PHBV matrix--effects of porosity and collagen dip coating.

In this study, we related porosity and collagen coating of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) scaffold to the degree of cell proliferation on the engineered PHBV scaffold. Based on the [3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2h-tetrazolium, inner salt] (MTS) assay, we established that UMR-106 cell proliferation is maximum in collagen-coated porous PHBV film followed by porous PHBV film and least in nonporous PHBV film. RT-PCR analysis of the proliferated cells on tissue culture polystyrene (TCPS) and porous and nonporous PHBV scaffolds revealed that the proliferated cells retained their osteoblastic phenotype characteristics. Atomic absorption analysis was performed to measure the extent of calcium conversion by the cells grown on PHBV and TCPS. The calcium content of the culture media was used to indirectly measure the mineralization ability of the cells. The extent of calcium conversion by the cells was found to depend on the incubation time. Based on the results of the study, modified PHBV matrix seems to be a suitable matrix candidate for bone tissue engineering application.

Langmuir adsorption study of the interaction of CdSe/ZnS quantum dots with model substrates: influence of substrate surface chemistry and pH.

We investigate the utility of Langmuir adsorption measurements for characterizing nanoparticle-substrate interactions. Spherical CdSe/ZnS core-shell nanoparticles were chosen as representative particles because of their widespread use in biological labeling measurements and their relatively monodisperse dimensions. In particular, the quantum dots were functionalized with 11-mercaptoundecanoic acid, and we utilized an amine-terminated self-assembled monolayer (SAM) as a model substrate. SAMs with different end-groups (-CH(3) and -COOH) were also considered to contrast with the adsorption behavior on the amine-terminated SAM substrates. We followed the kinetics of nanoparticle adsorption on the aminosilane layer by quartz crystal microgravimetry (QCM) over a range of particle concentrations and determined the corresponding Langmuir adsorption isotherms. Analysis of both equilibrium adsorption and kinetic adsorption data allowed us to determine a consistent value of the Langmuir adsorption equilibrium constant for the amine-terminated SAM at room temperature (K(L) approximately 2.7 (micromol/L)(-1)), providing a useful characterization of the nanoparticle-substrate interaction. The effect of varying solution pH on Langmuir adsorption was also investigated in order to gain insight into the role of electrostatic interactions on nanoparticle adsorption. The equilibrium extent of adsorption was found to be maximum at about pH 7. These changes of nanoparticle adsorption were further quantified and validated by X-ray photoelectron spectroscopy (XPS) and confocal fluorescence microscopy measurements. We conclude that Langmuir adsorption measurements provide a promising approach for quantifying nanoparticle-substrate interactions.