Thermal Diffusivity Determination of Protoporphyrin IX Solution Mixed with Gold Metallic Nanoparticles

Nanoparticles appear to be ideally suited for applications in targeted thermal effects in medical therapies and photothermally activated drug delivery; all depend critically on the thermal transport between the nanoparticles and the surrounding liquid. In this work thermal lens spectroscopy (TLS) was used to determine the thermal diffusivity of protoporphyrin IX (PpIX) solutions mixed with gold metallic nanoparticles. PpIX disodium salt (DS) was used in a HCl solution at 25%. Fluids containing gold (Au) nanoparticles at different concentrations were prepared and added to the PpIX solutions. For each solution, UV–Vis spectroscopy was used to obtain the optical absorption spectrum, and transmission electron microscopy (TEM) was used to obtain the gold nanoparticle size. From the TLS signal intensity, it was possible to determine the characteristic time constant of the transient thermal by fitting the theoretical expression to the experimental data. From this characteristic time, the thermal diffusivity was obtained for each solution. The results show that the thermal diffusivity of PpIX mixed with gold nanoparticles increases with an increase of the nanoparticle metallic concentration.     

Photothermal Study of Two Different Nanofluids Containing SiO2 and TiO2 Semiconductor Nanoparticles

Thermal and optical properties of two different nanofluids containing SiO₂ and TiO₂ semiconductor nanoparticles were studied by thermal lens spectrometry (TLS) and spectrophotometry. In the case of SiO₂ nanofluids the transmission electron microscopy technique was used to obtain the SiO₂ nanoparticle sizes to investigate the size effect of these nanoparticles on the sample thermal diffusivity which is important in some medical applications such as photothermal-modulated drug delivery systems. On the other hand for the case of TiO₂ nanofluids, the photopyroelectric technique, TLS, scanning electron microscopy, and X-ray diffraction were employed to investigate the concentration effect on the thermal properties of these nanofluids. Thermal diffusivities and effusivities as functions of the TiO₂ nanoparticle concentrations were obtained. From the experimental results, an incremental increase in the thermal diffusivities and effusivities was observed when the nanoparticle concentration was increased, indicating that the nanoparticle concentration is an important factor to be considered to obtain nanofluids with more thermal efficiency which are required for some applications, such as degradation of residual water.     

Thermal Characterization of Nanofluids with Different Solvents

Thermal lens spectrometry (TLS) and photopyroelectric (PPE) techniques were used to obtain the thermal diffusivity and effusivity of different nanofluid samples. The thermal effusivity of these samples was obtained by the PPE technique in a front detection configuration. In the case of the determination of the thermal diffusivity, TLS was used for the different solvents in the presence of gold nanoparticles (nanofluids). In this technique, an Ar⁺ laser and intensity stabilized He–Ne laser were used as the heating source and probe beam, respectively. The experimental results showed that thermal diffusivity values of the studied solvents (water, ethanol, and ethylene glycol) were enhanced by the presence of gold nanoparticles. Comparisons with literature values show good agreement with pure solvents. These techniques are applicable for all kind of liquid samples, including semitransparent ones.     

Thermal Diffusivity Measurements in Fluids Containing Metallic Nanoparticles using Transient Thermal Lens

Thermal diffusivity measurements are carried out in nanofluids, solutions containing gold nanoparticles (~ 10–40 nm size), using the mode-mismatched dual-beam thermal lens technique. An Ar+ laser is used as the heating source, and an intensity stabilized He–Ne laser serves as the probe beam. This technique provides a reliable photothermal alternative for measuring thermal diffusivities of nanofluids and semitransparent samples. The characteristic time constant of the transient thermal lens was obtained by fitting the experimental data to the theoretical expression for the transient thermal lens. From this characteristic time, the fluid thermal diffusivity, which increases when the particle sizes increase was obtained. The size of the nanoparticles was obtained from transmission electron microscopy (TEM) analysis.Paper presented at the Seventeenth European Conference on Thermophysical Properties, September 5–8, 2005, Bratislava, Slovak Republic.     

Monitoring the Thermal Parameters of Different Edible Oils by Using Thermal Lens Spectrometry

Several vegetable edible oils (sunflower, canola, soya, and corn) were used to study the thermal diffusivity of edible oils. Thermal lens spectrometry (TLS) was applied to measure the thermal properties. The results showed that the obtained thermal diffusivities with this technique have good agreement when compared with literature values. In this technique an Ar⁺ laser and intensity stabilized He–Ne laser were used as the heating source and probe beam, respectively. These studies may contribute to a better understanding of the physical properties of edible oils and the quality of these important foodstuffs.     

A Transient Heating Technique for Measuring the Thermal Diffusivity of Metals

A transient heating technique, improving the constant-rate-heating technique for the measurements of thermal diffusivities of metals, is proposed. For a physical model of a specimen to be measured, the transient heat-conduction equation was solved with some boundary conditions, and the solution obtained was used as the principle of the present transient heating technique for determining the thermal diffusivity of the specimen. Additionally, a thermal analysis was made to satisfy a boundary condition involved in the principle, that is, the condition of radiative thermal insulation at the two end surfaces of the specimen. To verify the validity of the present technique, the thermal diffusivity of iron, whose thermophysical properties are well-known, was measured with the same apparatus as used in our previous work, and the experimental results are discussed. Moreover, thermal diffusivities of thermocouple materials, namely, constantan, chromel, and alumel, were measured by the technique in the temperature range of 360 to 680 K.     

A Simple Investigation of the Thermal Effusivity of Silver Nanofluid Using Photopyroelectric Technique

We investigated the thermal effusivity of silver nanofluids using a microwave technique. During microwave irradiation, silver nanoparticles with a narrow particle size distribution were formed in water and in ethylene glycol, with a polyvinylpyrrolidone stabilizer. We designed and used a front-photopyroelectric technique that employed a metalized polyvinylidene difluoride (PVDF) pyroelectric sensor, with a thermally thick sensor and sample. Using this technique, we calculated the thermal effusivity of the silver nanofluids at a given frequency using the combination of the signal’s normalized amplitude–phase. The thermal effusivity of the nanofluids increased with the number of microwave irradiation cycles, which increased the nanoparticle concentration in the base fluids. A comparison with reported values illustrates the high accuracy obtained from the results of thermal diffusivity, the thermal effusivity of the PVDF sensor, and the thermal effusivity of ethylene glycol as a base fluid (differing by only 1.7 %, 0.5 %, and 2.3 %, respectively). Our method can therefore be used to study nanofluids with varying nanoparticle properties, such as concentration, size, and shape.     

Multichannel electrochemiluminescence of luminol in neutral and alkaline aqueous solutions on a gold nanoparticle self-assembled electrode

The electrochemiluminescence (ECL) behavior of luminol on a gold nanoparticle self-assembled electrode in neutral and alkaline pH conditions was studied under conventional cyclic voltammetry (CV). The gold nanoparticle self-assembled electrode exhibited excellent electrocatalytic property and redox reactivity to the luminol ECL system. In neutral solution, four ECL peaks were observed at 0.69, 1.03, -0.45, and -1.22 V (vs SCE) on the curve of ECL intensity versus potential. Compared with a bulk gold electrode, two anodic and one cathodic ECL peaks were greatly enhanced, and one new cathodic ECL peak appeared. In alkaline solution, two anodic ECL peaks were obtained at 0.69 and 1.03 V, which were much stronger than those on a bulk gold electrode. These ECL peaks were found to depend on gold nanoparticles on the surface of the electrode, potential scan direction and range, the presence of O(2) or N(2), the pH and concentration of luminol solution, NaBr concentration, and scan rate. The emitter of all ECL peaks was identified as 3-aminophthalate by analyzing the ECL spectra. The spatial distribution of the luminol ECL peaks on the gold nanoparticle self-assembled electrode was studied by CCD. The surface state of the gold nanoparticle self-assembled electrode was characterized by scanning electron microscopy (SEM) and UV-visible reflection spectra. The mechanism for the formation of these ECL peaks has been proposed. The results indicate that the gold nanoparticle self-assembled electrode could lead to novel ECL properties, and strong luminol ECL in neutral and alkaline solutions could be obtained on such an electrode, which is of great analytical potential.     

Anisotropic thermal diffusivity characterization of aligned carbon nanotube-polymer composites

The anisotropic thermal diffusivity of aligned carbon nanotube-polymer composites was determined using a photothermoelectric technique. The composites were obtained by infiltrating poly-dimethyl siloxane (PDMS) in aligned multiwall CNT arrays grown by chemical vapor deposition on silicon substrates. The thermal diffusivities are insensitive to temperature in the range of 180 K-300 K. The thermal diffusivity values across the alignment direction are approximately 2-4 times smaller than along the alignment direction and larger than effective media theory predictions using reported values for the thermal diffusivity of millimeter thick aligned multiwall carbon nanotube arrays. The effective room temperature thermal conductivity of the composite along the carbon nanotube alignment direction is at least 6X larger than the thermal conductivity of the polymer matrix and is in good agreement with the effective media predictions. This work indicates that infiltration of long and aligned carbon nanotube arrays is currently the most efficient method to obtain high thermal conductivity polymer composites.     

Dynamic light scattering and UV–vis spectroscopy of gold nanoparticles solution

Gold nanoparticles solution prepared in water by laser ablation at 1064 nm of a gold metal plate was characterized by dynamic light scattering and UV–vis spectroscopy. Polarized dynamic scattering allows the measurement of translational diffusivity of Au nanoparticles, while depolarized scattering yields simultaneously the characterization of translational and rotational diffusivities. From these measurements the size and shape of Au nanoparticles are determined. Dynamic light scattering yields an average radius of 32 nm for the spherical nanoparticles in as prepared solution. The same measurements performed in an aged solution reveal the formation of ellipsoidal nanoparticles with minor and major semi-axis of 36 nm and 69 nm, respectively. The measured values allow to fit the UV–vis spectra with the Mie-Gans model and to measure the concentration of Au nanoparticles obtaining a complete characterization of their nanostructure. Dynamic light scattering results a powerful technique to characterize the size and shape of gold nanoparticles.     

Multidimensional Flash Diffusivity Measurements of Orthotropic Materials

A generalization of the radial flash technique is presented whereby the thermal diffusivity of an orthotropic solid is measured in directions parallel and perpendicular to the flash source. The theoretical formulation is based on a Green's function approach which assumes a general orthotropic solid with three mutually orthogonal thermal diffusivities (or conductivities). Using this approach, a solution to this problem is presented which can be used to develop solutions for arbitrary pulse waveforms and incident geometries. Analytical and numerical results are presented for two-dimensional and three-dimensional cases of finite and semiinfinite solids. Characteristic equations which describe the ratio of the temperatures at two points along a principal axis are given. The equations show excellent agreement with numerical predictions as well as experimental results. A parameter estimation approach is given which improves on the accuracy of the radial flash technique in the determination of thermal diffusivity from experimental data.     

Photothermal Techniques Applied to the Thermal Characterization of l–Cysteine Nanofluids

Thermal-diffusivity (D) and thermal-effusivity (e) measurements were carried out in l-cysteine nanoliquids l-cysteine in combination with Au nanoparticles and protoporphyrin IX (PpIX) nanofluid) by using thermal lens spectrometry (TLS) and photopyroelectric (PPE) techniques. The TLS technique was used in the two mismatched mode experimental configuration to obtain the thermal-diffusivity of the samples. On the other hand, the sample thermal effusivity (e) was obtained by using the PPE technique where the temperature variation of a sample, exposed to modulated radiation, is measured with a pyrolectric sensor. From the obtained thermal-diffusivity and thermal-effusivity values, the thermal conductivity and specific heat capacity of the sample were calculated. The obtained thermal parameters were compared with the thermal parameters of water. The results of this study could be applied to the detection of tumors by using the l-cysteine in combination with Au nanoparticles and PpIX nanofluid, called conjugated in this study.     

Thermal Properties of Porcine Tissues Determined by Modified Photoacoustic Piezoelectric Technique

Using the modified photoacoustic piezoelectric (PAPE) technique, the influence of the piezoelectric transducer on the vibrations of the sample is taken into account. The modified PAPE technique is employed to determine the average thermal diffusivities of the porcine tissues, which include fresh and dry skin, fat, and muscle. The values of the thermal diffusivities of all measured porcine tissues determined by the modified PAPE technique are smaller than those of the conventional ones, especially for the dry skin and fresh fat samples. The thermal diffusivity of the fresh skin sample is the biggest, and the dry samples of different tissues have similar thermal properties with each other. These results show that the modified PAPE technique can provide thermal characterization of the porcine tissues more effectively.     

Measurement of the Thermal Diffusivity of Solids with an Improved Accuracy

A photothermal radiometry technique is being developed at the NPL with the goal of improving the accuracy of thermal diffusivity measurements. The principle is to perform a laser-induced thermal experiment while simultaneously making accurate measurements of the experimental boundary conditions. A numerical three-dimensional heat diffusion model based on thermal transfer functions has been developed to account for the measured boundary conditions. The thermal diffusivity is determined from the experimental data by a nonlinear, least-squares fit to the model. Experiments carried out on pure metals at 900 K demonstrate good agreement between the theoretical predictions and experimental data, and uncertainties of about 1.5% for the thermal diffusivities of platinum, titanium, and germanium were obtained.     

Gold nanoparticle-modified etched capillaries for open-tubular capillary electrochromatography

The use of gold nanoparticles in conjunction with etched capillary-based open-tubular capillary electrochromatography (OTCEC) to improve the efficiency of separation and the selectivity between selected solutes is described. The fused-silica capillaries (50-microm i.d.) were etched with ammonium hydrogen difluoride, followed by prederivatization of the new surface with (3-mercaptopropyl)trimethoxysilane (MPTMS) for the immobilization of dodecanethiol gold nanoparticles, for OTCEC. The electrochromatography of a "reversed-phase" test mixture and of selected polycylic aromatic hydrocarbons was investigated, and efficient separations and high theoretical plate numbers per meter were obtained. The electroosmotic flow characteristics of the etched gold nanoparticle capillary, unetched gold nanoparticle capillary, bare capillary, and etched bare capillary were studied by varying the percentage of organic modifier in buffer, buffer pH, and separation voltage. Optical microscopy and scanning electron microscopy were used to examine the process of etching and modification and the surface features of the etched gold nanoparticle capillary. The results confirm that dodecanethiol gold nanoparticles bonded on the etched inner wall of the fused-silica capillary can provide sufficient solute-bonded phase interactions to obtain OTCEC separations with reproducible retention, as well as characteristic reversed-phase behavior, even with the inner diameter of the capillary of 50 microm.     

Evaluation of the Heat Leakage in the Thermal Diffusivity Measurement of Molten Metals by a Laser Flash Method

Evaluation of the radiative and conductive heat loss from a molten metal sample to the cell has been made in order to obtain accurate thermal diffusivities of molten metals at high temperature with a laser flash method. The results suggest that thermal diffusivity values of molten nickel can be determined in the temperature range from 1728 to 1928 K with an uncertainty of ±3% in comparison with case considering only the effect of radiative heat loss. The usefulness of a cell for a laser flash method has been confirmed by applying simulated results to evaluate the heat leakage in the thermal diffusivity measurement of molten metals.     

Experimental Verification to Obtain Intrinsic Thermal Diffusivity by Laser-Flash Method

There is a need to obtain highly reliable values of thermophysical properties. The thermal conductivity of solids is often calculated from the thermal diffusivity, specific heat, and density, respectively, measured by the laser-flash method, differential scanning calorimetry, and Archimedes’ method. The laser-flash method is one of the most well-known methods for measuring the thermal diffusivity of solids above room temperature. This method is very convenient to measure the thermal diffusivity without contact in a short time. On the other hand, it is considered as an absolute reference measurement method, in particular, because only measurements of basic quantities such as time, temperature, length, and electrical quantities are required, and because the uncertainty of measurement can be analytically evaluated. However, it could be difficult in some cases to obtain reliable thermal-diffusivity values. The measurement results can indeed depend on experimental conditions; in particular, the pulse heating energy. A procedure to obtain the intrinsic thermal-diffusivity value was proposed by National Metrology Institute of Japan (NMIJ). Here, “intrinsic” means unique for the material, independent of measurement conditions. In this method, apparent thermal-diffusivity values are first measured by changing the pulse heating energy at the same test temperature. Then, the intrinsic thermal diffusivity is determined by extrapolating these apparent thermal diffusivities to a zero energy pulse. In order to verify and examine the applicability of the procedure for intrinsic thermal-diffusivity measurements, we have measured the thermal diffusivity of some materials (metals, ceramics) using the laser-flash method with this extrapolation procedure. NMIJ and Laboratoire National de Metrologie et d’essais (LNE) have laser-flash thermal-diffusivity measurement systems that are traceable to SI units. The thermal diffusivity measured by NMIJ and LNE on four materials shows good agreement, although they used different measurement systems and different analysis methods of the temperature-rise curve. Experimental verification on the procedure was carried out using the measured results. Some problems and considered solutions for laser-flash thermal-diffusivity measurements are discussed.     

Thermal Characterization of Edible Oils by Using Photopyroelectric Technique

Thermal properties of several edible oils such as olive, sesame, and grape seed oils were obtained by using the photopyroelectric technique. The inverse photopyroelectric configuration was used in order to obtain the thermal effusivity of the oil samples. The theoretical equation for the photopyroelectric signal in this configuration, as a function of the incident light modulation frequency, was fitted to the experimental data in order to obtain the thermal effusivity of these samples. Also, the back photopyroelectric configuration was used to obtain the thermal diffusivity of these oils; this thermal parameter was obtained by fitting the theoretical equation for this configuration, as a function of the sample thickness (called the thermal wave resonator cavity), to the experimental data. All measurements were done at room temperature. A complete thermal characterization of these edible oils was achieved by the relationship between the obtained thermal diffusivities and thermal effusivities with their thermal conductivities and volumetric heat capacities. The obtained results are in agreement with the thermal properties reported for the case of the olive oil.     

Highly stable,protein capped gold nanoparticles as effective drug delivery vehicles for amino-glycosidic antibiotics

A method for the production of highly stable gold nanoparticles (Au NP) was optimized using sodium borohydride as reducing agent and bovine serum albumin as capping agent. The synthesized nanoparticles were characterized using UV–visible spectroscopy, transmission electron microscopy, X‐ray diffraction (XRD) and dynamic light scattering techniques. The formation of gold nanoparticles was confirmed from the appearance of pink colour and an absorption maximum at 532 nm. These protein capped nanoparticles exhibited excellent stability towards pH modification and electrolyte addition. The produced nanoparticles were found to be spherical in shape, nearly monodispersed and with an average particle size of 7.8 ± 1.7 nm. Crystalline nature of the nanoparticles in face centered cubic structure is confirmed from the selected‐area electron diffraction and XRD patterns. The nanoparticles were functionalized with various amino-glycosidic antibiotics for utilizing them as drug delivery vehicles. Using Fourier transform infrared spectroscopy, the possible functional groups of antibiotics bound to the nanoparticle surface have been examined. These drug loaded nanoparticle solutions were tested for their antibacterial activity against Gram-negative and Gram-positive bacterial strains, by well diffusion assay. The antibiotic conjugated Au NP exhibited enhanced antibacterial activity, compared to pure antibiotic at the same concentration. Being protein capped and highly stable, these gold nanoparticles can act as effective carriers for drugs and might have considerable applications in the field of infection prevention and therapeutics.     

pH-Dependent gold nanoparticle self-organization on functionalized Si/SiO2 surfaces

The self-organization of citrate- and acrylate-stabilized gold nanoparticles onto SiO₂/hydroxyl-, amino- and nitro-terminated surfaces was investigated as a function of pH. Bare clean Si/SiO₂ substrates were used as the SiO₂/hydroxyl-terminated surfaces and self-assembled monolayers (SAM) of (3-aminopropyl)trimethoxysilane (APTMS) and 3-(4-nitrophenoxy)-propyltrimethoxysilane (NPPTMS) on Si/SiO₂ were employed as the amino- and nitro-terminated surfaces, respectively. All the surfaces were fully characterized by contact angle, atomic force microscopy (AFM), ellipsometry and X-ray photoelectron spectroscopy (XPS). Citrate- and acrylate-stabilized gold nanoparticle stability was also investigated as a function of pH by UV–visible absorption spectroscopy and Z-potentiometry. The gold nanoparticle surface coverage of the substrates was independently estimated by AFM and XPS. The results show that colloid deposition on bare SiO₂/OH surfaces and on NPPTMS monolayers is negligible with the exception of acrylate-stabilized gold nanoparticles which were found to be immobilized on nitro-terminated surfaces at pH lower than 3.5. Nevertheless, APTMS monolayers interact strongly with citrate- and acrylate-stabilized gold nanoparticles exhibiting a dependence of the surface coverage from the pH of the colloidal solution.