Temperature-controlled spectrophotometry: a simultaneous analysis of phase transition, thermal degradation and optical properties of semi-transparent composites from 20 °C to 450 °C.

So far, optical and effective radiative properties of polymer matrix based composites were investigated at temperatures well below their degradation temperature. At the same time, polymers exhibit temperature dependent physical properties and may undergo structural changes as their temperature raises. In this work, we employ the "Temperature-Controlled Spectrophotometry", a new method enabling to identify simultaneously phase transitions, thermal degradation and radiative properties of semi-transparent composites over a large temperature range. The method consists of measuring simultaneously the normal-normal and the normal-hemispherical transmittances and reflectances of the sample subjected to a laser irradiation with tuneable wavelength while the temperature is rised from room temperature up to 450 °C by means of a CO2 laser. Physical changes of the sample are identified from the temperature variation of normal-normal transmittance and specular reflectance measurements. Most of the results here are presented at a specific wavelength of 1070 nm but the proposed method is suitable over the semi-transparency spectral domain of the material by changing the wavelength of the probe laser. An inverse method for parameter identification based on normal-hemispherical measurements is employed to determine the transport effective radiative properties of the sample, namely the transport extinction coefficient and the transport scattering albedo from room temperature to 325 °C.

Curvature and temperature-dependent thermal interface conductance between nanoscale gold and water.

Plasmonic gold nanoparticles (AuNPs) can convert laser irradiation into thermal energy for a variety of applications. Although heat transfer through the AuNP-water interface is considered an essential part of the plasmonic heating process, there is a lack of mechanistic understanding of how interface curvature and the heating itself impact interfacial heat transfer. Here, we report atomistic molecular dynamics simulations that investigate heat transfer through nanoscale gold-water interfaces. We simulated four nanoscale gold structures under various applied heat flux values to evaluate how gold-water interface curvature and temperature affect the interfacial heat transfer. We also considered a case in which we artificially reduced wetting at the gold surfaces by tuning the gold-water interactions to determine if such a perturbation alters the curvature and temperature dependence of the gold-water interfacial heat transfer. We first confirmed that interfacial heat transfer is particularly important for small particles (diameter ≤10 nm). We found that the thermal interface conductance increases linearly with interface curvature regardless of the gold wettability, while it increases nonlinearly with the applied heat flux under normal wetting and remains constant under reduced wetting. Our analysis suggests the curvature dependence of the interface conductance coincides with changes in interfacial water adsorption, while the temperature dependence may arise from temperature-induced shifts in the distribution of water vibrational states. Our study advances the current understanding of interface thermal conductance for a broad range of applications.

Computational Investigation of Protein Photoinactivation by Molecular Hyperthermia.

To precisely control protein activity in a living system is a challenging yet long-pursued objective in biomedical sciences. Recently, we have developed a new approach named molecular hyperthermia (MH) to photoinactivate protein activity of interest without genetic modification. MH utilizes nanosecond laser pulse to create nanoscale heating around plasmonic nanoparticles to inactivate adjacent protein in live cells. Here we use a numerical model to study important parameters and conditions for MH to efficiently inactivate proteins in nanoscale. To quantify the protein inactivation process, the impact zone is defined as the range where proteins are inactivated by the nanoparticle localized heating. Factors that reduce the MH impact zone include the laser pulse duration, temperature-dependent thermal conductivity (versus constant properties), and nonspherical nanoparticle geometry. In contrast, the impact zone is insensitive to temperature-dependent material density and specific heat, as well as thermal interface resistance based on reported data in the literature. The low thermal conductivity of cytoplasm increases the impact zone. Different proteins with various Arrhenius kinetic parameters have significantly different impact zones. This study provides guidelines to design the protein inactivation process by MH.

Monte Carlo prediction of ballistic effect on phonon transport in silicon in the presence of small localized heat source.

Understanding phonon transport at nanoscale is critically important for thermal nanometrology applications including scanning thermal microscopy, three-omega and time domain thermoreflectance experiments. In this paper, a multidimensional non-gray Monte Carlo simulation is developed to investigate the ballistic phonon transport in a silicon sample heated on the top by a small localized heater line. We observed that heat confinement occurs for very small heat sources. This result contradicts the classical Fourier model, according to which the heat penetration depth is always significant, even with small sources. The temperature fields inside the sample exhibit different penetration depths depending strongly on the heater line size. Maximum thermal resistance and a large interface temperature jump take place in the limit of very small heater width compared to the phonon mean free path due to the nonequilibrium and ballistic nature of phonon transport. Increasing the heater width leads to a decrease in the heat flux and temperature jump. In the limit of a very large heat source, the heat flux and temperature jump become independent of heat source size. In accordance with experimental investigations for the case of sapphire material (Siemens et al 2010 Nature Mat. 9 26-30), the thermal resistance of the silicon sample due to the localized heat source decreases and then tends to reach a plateau with increasing source size from tens of nanometers to micrometers. These results are important, not only for understanding the thermal transport in the sample during nanometrology experiments, but also for the design and manipulation of heat at nanoscale.

Optical properties of oakwood in the near-infrared range of semi-transparency.

The spectral absorption and scattering properties of oakwood are retrieved from the measurements of both the normal-hemispherical reflectance and transmittance in the visible and near-infrared ranges of semi-transparency. We employ two alternative methods for the radiative transfer in wood samples: the modified two-flux approximation and the high-order discrete ordinate method. The modifications of both methods take into account the effect of total internal reflection at both surfaces of the wood samples. The analytical approximate solution of the first method gives very accurate results for the absorption coefficient, but the transport scattering coefficient of wood appeared to be systematically underestimated. Fortunately, this error is between 7% and 12%, and that is acceptable for the estimates. The oakwood samples of four different thicknesses were used in the experiments. The effect of the wood cell orientation appears to be insignificant and can be observed in the reflectance from optically thin samples only. There is a considerable decrease in the transport scattering coefficient of oakwood with the wavelength. This effect is explained by a predominant contribution of micron-sized longitudinal pores in oakwood. The latter is used to develop an approximate theoretical model of scattering based on the rigorous solution for arbitrary-oriented cylindrical pores. The model suggested is in good agreement with the experimental data.

Effect of pore-level geometry on far-field radiative properties of three-dimensionally ordered macroporous ceria particle.

The effects of pore size on direction-averaged radiative properties of three-dimensionally ordered macroporous (3DOM) cerium dioxide (ceria) particles are investigated in the spectral range of 0.3-10 µm. The particles are of spherical shape and contain interconnected pores in a face-centered cubic lattice arrangement. The porous particle is modeled as a three-dimensional array of interacting dipoles using the discrete dipole approximation (DDA). The validity of the Lorenz-Mie theory to predict far-field radiative properties of a quasi-homogeneous particle with the effective optical properties obtained using the volume-averaging theory (VAT) is demonstrated. Direction-averaged extinction, scattering, and absorption efficiency factors as well as the scattering asymmetry factor are determined as a function of the pore size for a particle of 1 µm diameter and as a function of the particle size for pores of 400 nm diameter. The overlapping ordered pores in the 3DOM particles and the boundary effects in the presence of pores of size comparable to that of the particle are shown to affect the radiative properties in the ultraviolet to near-infrared spectral ranges. The effects of the 3DOM pore-level features on the far-field radiative properties are not captured by the Lorenz-Mie theory combined with VAT. Consequently, the use of advanced modeling tools such as DDA is necessary. In the mid- and far-infrared spectral ranges, the effects of 3DOM pore-level features on the far-field radiative properties diminish and the approach combining the Lorenz-Mie theory and VAT is shown to be accurate.

Enhanced Nanobubble Formation: Gold Nanoparticle Conjugation to Qß Virus-like Particles.

Plasmonic gold nanostructures are a prevalent tool in modern hypersensitive analytical techniques such as photoablation, bioimaging, and biosensing. Recent studies have shown that gold nanostructures generate transient nanobubbles through localized heating and have been found in various biomedical applications. However, the current method of plasmonic nanoparticle cavitation events has several disadvantages, specifically including small metal nanostructures (≤10 nm) which lack size control, tuneability, and tissue localization by use of ultrashort pulses (ns, ps) and high-energy lasers which can result in tissue and cellular damage. This research investigates a method to immobilize sub-10 nm AuNPs (3.5 and 5 nm) onto a chemically modified thiol-rich surface of Qß virus-like particles. These findings demonstrate that the multivalent display of sub-10 nm gold nanoparticles (AuNPs) caused a profound and disproportionate increase in photocavitation by upward of 5-7-fold and significantly lowered the laser fluency by 4-fold when compared to individual sub-10 nm AuNPs. Furthermore, computational modeling showed that the cooling time of QßAuNP scaffolds is significantly extended than that of individual AuNPs, proving greater control of laser fluency and nanobubble generation as seen in the experimental data. Ultimately, these findings showed how QßAuNP composites are more effective at nanobubble generation than current methods of plasmonic nanoparticle cavitation.

X-ray Tomography Coupled with Finite Elements, A Fast Method to Design Aerogel Composites and Prove Their Superinsulation Experimentally.

Composite aerogels can include fibers, opacifiers and binders but are rarely designed and optimized to achieve the best thermal/mechanical efficiency. This paper proposes a three-dimensional X-ray tomography-based method for designing composites. Two types of models are considered: classical and inexpensive homogenization models and more refined finite element models. XrFE is based on the material's real three-dimensional microstructure and/or its twin numerical microstructure, and calculates the effective conductivity of the material. First, the three-dimensional sample is meshed and labeled. Then, a finite element method is used to calculate the heat flow in the samples. The entire three-dimensional microstructure of a real or fictitious sample is thus associated with a heat flow and an effective conductivity. Parametric studies were performed to understand the relationship between microstructure and thermal efficiency. They highlighted how quickly a low volume fraction addition can improve or ruin thermal conductivity. A reduced set of three formulations was developed and fully characterized. The mechanical behavior was higher than 50 KPa, with thermal efficiencies ranging from 14 to 15 mW·m·K−1.

Single pulse heating of a nanoparticle array for biological applications.

With the ability to convert external excitation into heat, nanomaterials play an essential role in many biomedical applications. Two modes of nanoparticle (NP) array heating, nanoscale-confined heating (NCH) and macroscale-collective heating (MCH), have been found and extensively studied. Despite this, the resulting biological response at the protein level remains elusive. In this study, we developed a computational model to systematically investigate the single-pulsed heating of the NP array and corresponding protein denaturation/activation. We found that NCH may lead to targeted protein denaturation, however, nanoparticle heating does not lead to nanoscale selective TRPV1 channel activation. The excitation duration and NP concentration are primary factors that determine a window for targeted protein denaturation, and together with heating power, we defined quantified boundaries for targeted protein denaturation. Our results boost our understandings of the NCH and MCH under realistic physical constraints and provide robust guidance to customize biomedical platforms with desired NP heating.

Nanoparticle Fragmentation Below the Melting Point Under Single Picosecond Laser Pulse Stimulation.

Understanding the laser-nanomaterials interaction including nanomaterial fragmentation has important implications in nanoparticle manufacturing, energy, and biomedical sciences. So far, three mechanisms of laser-induced fragmentation have been recognized including non-thermal processes and thermomechanical force under femtosecond pulses, and the phase transitions under nanosecond pulses. Here we show that single picosecond (ps) laser pulse stimulation leads to anomalous fragmentation of gold nanoparticles that deviates from these three mechanisms. The ps laser fragmentation was weakly dependent on particle size, and it resulted in a bimodal size distribution. Importantly, ps laser stimulation fragmented particles below the whole particle melting point and below the threshold for non-thermal mechanism. We propose a framework based on near-field enhancement and nanoparticle surface melting to account for the ps laser-induced fragmentation observed here. This study reveals a new form of surface ablation that occurs under picosecond laser stimulation at low fluence.

Transient Photoinactivation of Cell Membrane Protein Activity without Genetic Modification by Molecular Hyperthermia.

Precise manipulation of protein activity in living systems has broad applications in biomedical sciences. However, it is challenging to use light to manipulate protein activity in living systems without genetic modification. Here, we report a technique to optically switch off protein activity in living cells with high spatiotemporal resolution, referred to as molecular hyperthermia (MH). MH is based on the nanoscale-confined heating of plasmonic gold nanoparticles by short laser pulses to unfold and photoinactivate targeted proteins of interest. First, we show that protease-activated receptor 2 (PAR2), a G-protein-coupled receptor and an important pathway that leads to pain sensitization, can be photoinactivated in situ by MH without compromising cell proliferation. PAR2 activity can be switched off in laser-targeted cells without affecting surrounding cells. Furthermore, we demonstrate the molecular specificity of MH by inactivating PAR2 while leaving other receptors intact. Second, we demonstrate that the photoinactivation of a tight junction protein in brain endothelial monolayers leads to a reversible blood-brain barrier opening in vitro. Lastly, the protein inactivation by MH is below the nanobubble generation threshold and thus is predominantly due to the nanoscale heating. MH is distinct from traditional hyperthermia (that induces global tissue heating) in both its time and length scales: nanoseconds versus seconds, nanometers versus millimeters. Our results demonstrate that MH enables selective and remote manipulation of protein activity and cellular behavior without genetic modification.

Tuning the Gold Nanoparticle Colorimetric Assay by Nanoparticle Size, Concentration, and Size Combinations for Oligonucleotide Detection.

Gold nanoparticle (GNP)-based aggregation assay is simple, fast, and employs a colorimetric detection method. Although previous studies have reported using GNP-based colorimetric assay to detect biological and chemical targets, a mechanistic and quantitative understanding of the assay and effects of GNP parameters on the assay performance is lacking. In this work, we investigated this important aspect of the GNP aggregation assay including effects of GNP concentration and size on the assay performance to detect malarial DNA. Our findings lead us to propose three major competing factors that determine the final assay performance including the nanoparticle aggregation rate, plasmonic coupling strength, and background signal. First, increasing nanoparticle size reduces the Brownian motion and thus aggregation rate, but significantly increases plasmonic coupling strength. We found that larger GNP leads to stronger signal and improved limit of detection (LOD), suggesting a dominating effect of plasmonic coupling strength. Second, higher nanoparticle concentration increases the probability of nanoparticle interactions and thus aggregation rate, but also increases the background extinction signal. We observed that higher GNP concentration leads to stronger signal at high target concentrations due to higher aggregation rate. However, the fact the optimal LOD was found at intermediate GNP concentrations suggests a balance of two competing mechanisms between aggregation rate and signal/background ratio. In summary, our work provides new guidelines to design GNP aggregation-based POC devices to meet the signal and sensitivity needs for infectious disease diagnosis and other applications.

Quantitative Comparison of Photothermal Heat Generation between Gold Nanospheres and Nanorods.

Gold nanoparticles (GNPs) are widely used for biomedical applications due to unique optical properties, established synthesis methods, and biological compatibility. Despite important applications of plasmonic heating in thermal therapy, imaging, and diagnostics, the lack of quantification in heat generation leads to difficulties in comparing the heating capability for new plasmonic nanostructures and predicting the therapeutic and diagnostic outcome. This study quantifies GNP heat generation by experimental measurements and theoretical predictions for gold nanospheres (GNS) and nanorods (GNR). Interestingly, the results show a GNP-type dependent agreement between experiment and theory. The measured heat generation of GNS matches well with theory, while the measured heat generation of GNR is only 30% of that predicted theoretically at peak absorption. This then leads to a surprising finding that the polydispersity, the deviation of nanoparticle size and shape from nominal value, significantly influences GNR heat generation (>70% reduction), while having a limited effect for GNS (<10% change). This work demonstrates that polydispersity is an important metric in quantitatively predicting plasmonic heat generation and provides a validated framework to quantitatively compare the heating capabilities between gold and other plasmonic nanostructures.

Modeling radiation characteristics of semitransparent media containing bubbles or particles.

Modeling of radiation characteristics of semitransparent media containing particles or bubbles in the independent scattering limit is examined. The existing radiative properties models of a single particle in an absorbing medium using the approaches based on (1) the classical Mie theory neglecting absorption by the matrix, (2) the far field approximation, and (3) the near field approximation are reviewed. Comparison between models and experimental measurements are carried out not only for the radiation characteristics but also for hemispherical transmittance and reflectance of porous fused quartz. Large differences are found among the three models predicting the bubble radiative properties when the matrix is strongly absorbing and/or the bubbles are optically large. However, these disagreements are masked by the matrix absorption during calculation of radiation characteristics of the participating medium. It is shown that all three approaches can be used for radiative transfer calculations in an absorbing matrix containing bubbles.

Modified two-flux approximation for identification of radiative properties of absorbing and scattering media from directional-hemispherical measurements.

A modified two-flux approximation is suggested for calculating the hemispherical transmittance and reflectance of a refracting, absorbing, and scattering medium in the case of collimated irradiation of the sample along the normal to the interface. The Fresnel reflection is taken into account in this approach. It is shown that the new approximation is rather accurate for the model transport scattering function. For an arbitrary scattering medium, the error of the modified two-flux approximation is estimated by comparison with the exact numerical calculations for the Henyey-Greenstein scattering function in a wide range of albedos and optical thicknesses. Possible applications of the derived analytical solution to identification problems are discussed.

Use of Mie theory to analyze experimental data to identify infrared properties of fused quartz containing bubbles.

An improved method used to determine the absorption and scattering characteristics of a weakly absorbing substance containing bubbles is suggested. The identification procedure is based on a combination of directional-hemispherical measurements and predictions of Mie-scattering theory including approximate relations for a medium with polydisperse bubbles. A modified two-flux approximation is suggested for the calculation of directional-hemispherical transmittance and reflectance of a refracting and scattering medium. The complete identification procedure gives not only the spectral radiative properties but also the volume fraction of bubbles and the characteristics of possible impurity of the medium. This procedure is used to obtain new data on near-infrared properties of fused-quartz samples containing bubbles.