Effect of handling and fixation processes on fluorescence spectroscopy of mouse skeletal muscles under two-photon excitation

We investigated the effects of handling and fixation processes on the two-photon fluorescence spectroscopy of endogenous fluorophors in mouse skeletal muscle. The skeletal muscle was handled in one of two ways: either sectioned without storage or sectioned following storage in a freezer. The two-photon fluorescence spectra measured for different storage or fixation periods show a differential among those samples that were stored in water or were fixed either in formalin or methanol. The spectroscopic results indicate that formalin was the least disruptive fixative, having only a weak effect on the two-photon fluorescence spectroscopy of muscle tissue, whereas methanol had a significant influence on one of the autofluorescence peaks. The two handling processes yielded similar spectral information, indicating no different effects between them.

Two-photon fluorescence spectroscopy for identification of healthy and malignant biological tissues

Two-photon fluorescence spectroscopy has been performed on rat skeletal muscles to investigate the effect of fixation processes on the micro-environments of the endogenous fluorophors in rat skeletal muscles. The two-photon fluorescence spectra measured for different fixation periods show a differential among those samples that were fixed in water, formalin and methanol, respectively. The results imply that two-photon fluorescence spectroscopy can be a potential technique for identification of healthy and malignant biological tissues.

Removal of methyl orange from aqueous solutions through adsorption by calcium aluminate hydrates

Methyl orange (MO) is a kind of anionic dye and widely used in industry. In this study, tricalcium aluminate hydrates (Ca-Al-LDHs) are used as an adsorbent to remove methyl orange (MO) from aqueous solutions. The resulting products were studied by X-ray diffraction (XRD), infrared spectroscopy (MIR), thermal analysis (TG-DTA) and scanning electron microscope (SEM). The XRD results indicated that the MO molecules were successfully intercalated into the tricalcium aluminate hydrates, with the basal spacing of Ca-Al-LDH expanding to 2.48 nm. The MIR spectrum for CaAl-MO-LDH shows obvious bands assigned to the N@N, N@H stretching vibrations and S@O, SO_ 3 group respectively, which are considered as marks to assess MO_ ion intercalation into the interlayers of LDH. The overall morphology of CaAl-MOLDH displayed a ‘‘honey-comb’’ like structure, with the adjacent layers expanded.

A novel identification method for ultra trace detection of biomolecules using functionalised Surface Enhanced Raman Spectroscopy (SERS)

This thesis developed a new method for measuring extremely low amounts of organic and biological molecules, using Surface enhanced Raman Spectroscopy. This method has many potential applications, e.g. medical diagnosis, public health, food provenance, antidoping, forensics and homeland security. The method development used caffeine as the small molecule example, and erythropoietin (EPO) as the large molecule. This method is much more sensitive and specific than currently used methods; rapid, simple and cost effective. The method can be used to detect target molecules in beverages and biological fluids without the usual preparation steps.

Ultra sensitive label free surface enhanced Raman spectroscopy method for the detection of biomolecules

We present a proof of concept for a novel nanosensor for the detection of ultra-trace amounts of bio-active molecules in complex matrices. The nanosensor is comprised of gold nanoparticles with an ultra-thin silica shell and antibody surface attachment, which allows for the immobilization and direct detection of bio-active molecules by surface enhanced Raman spectroscopy (SERS) without requiring a Raman label. The ultra-thin passive layer (~1.3 nm thickness) prevents competing molecules from binding non-selectively to the gold surface without compromising the signal enhancement. The antibodies attached on the surface of the nanoparticles selectively bind to the target molecule with high affinity. The interaction between the nanosensor and the target analyte result in conformational rearrangements of the antibody binding sites, leading to significant changes in the surface enhanced Raman spectra of the nanoparticles when compared to the spectra of the un-reacted nanoparticles. Nanosensors of this design targeting the bio-active compounds erythropoietin and caffeine were able to detect ultra-trace amounts the analyte to the lower quantification limits of 3.5×10−13 M and 1×10−9 M, respectively.

Crystalline Si nanoparticles below crystallization threshold : effects of collisional heating in non-thermal atmospheric-pressure microplasmas

Nucleation and growth of highly crystalline silicon nanoparticles in atmospheric-pressure low-temperature microplasmas at gas temperatures well below the Si crystallization threshold and within a short (100 μs) period of time are demonstrated and explained. The modeling reveals that collision-enhanced ion fluxes can effectively increase the heat flux on the nanoparticle surface and this heating is controlled by the ion density. It is shown that nanoparticles can be heated to temperatures above the crystallization threshold. These combined experimental and theoretical results confirm the effective heating and structure control of Si nanoparticles at atmospheric pressure and low gas temperatures.

Effect of Coulomb blockade, gold resistance, and thermal expansion on the electrical resistance of ultrathin gold films

Controlling the electrical resistance of granular thin films is of great importance for many applications, yet a full understanding of electron transport in such films remains a major challenge. We have studied experimentally and by model calculations the temperature dependence of the electrical resistance of ultrathin gold films at temperatures between 2 K and 300 K. Using sputter deposition, the film morphology was varied from a discontinuous film of weakly coupled meandering islands to a continuous film of strongly coupled coalesced islands. In the weak-coupling regime, we compare the regular island array model, the cotunneling model, and the conduction percolation model with our experimental data. We show that the tunnel barriers and the Coulomb blockade energies are important at low temperatures and that the thermal expansion of the substrate and the island resistance affect the resistance at high temperatures. At low temperatures our experimental data show evidence for a transition from electron cotunneling to sequential tunneling but the data can also be interpreted in terms of conduction percolation. The resistivity and temperature coefficient of resistance of the meandering gold islands are found to resemble those of gold nanowires. We derive a simple expression for the temperature at which the resistance changes from non-metal-like behavior into metal-like behavior. In the case of strong island coupling, the total resistance is solely determined by the Ohmic island resistance.

Synthesis and structural properties of Al-C-N-O composite thin films

Al-C-N-O composite thin films have been synthesized by radio frequency reactive diode sputtering of an aluminum target in plasmas of N2+O2+CH4 gas mixtures. The chemical structure and composition of the films have been investigated by means of infrared and X-ray photoelectron spectroscopy. The results reveal the formation of C-N, Al-C, Al-N and Al-O bonds. The X-ray diffraction pattern suggests that the films are of nanometer composite material and contain predominately crystalline grains of hexagonal AlN and α-Al2O3. A good thermal stability of the composite has been confirmed by the annealing treatment at temperatures up to 600 °C.

Structure-mediated thermal transport of monolayer graphene allotropes nanoribbons

We report the study of the thermal transport management of monolayer graphene allotrope nanoribbons (size ∼20 × 4 nm2) by the modulation of their structures via molecular dynamics simulations. The thermal conductivity of graphyne (GY)-like geometries is observed to decrease monotonously with increasing number of acetylenic linkages between adjacent hexagons. Strikingly, by incorporating those GY or GY-like structures, the thermal performance of graphene can be effectively engineered. The resulting hetero-junctions possess a sharp local temperature jump at the interface, and show a much lower effective thermal conductivity due to the enhanced phonon–phonon scattering. More importantly, by controlling the percentage, type and distribution pattern of the GY or GY-like structures, the hetero-junctions are found to exhibit tunable thermal transport properties (including the effective thermal conductivity, interfacial thermal resistance and rectification). This study provides a heuristic guideline to manipulate the thermal properties of 2D carbon networks, ideal for application in thermoelectric devices with strongly suppressed thermal conductivity.

Thermal effect of plasmon oscillations on the tunnel current in gold nanoisland thin film at low laser intensity

The effect of plasmon oscillations on the DC tunnel current in a gold nanoisland thin film (GNITF) is investigated using low intensity P~1W/cm2 continuous wave lasers. While DC voltages (1–150 V) were applied to the GNITF, it was irradiated with lasers at different wavelengths (k¼473, 532, and 633 nm). Because of plasmon oscillations, the tunnel current increased. It is found that the tunnel current enhancement is mainly due to the thermal effect of plasmon oscillations rather than other plasmonic effects. The results are highly relevant to applications of plasmonic effects in opto-electronic devices.

Prediction of thermal expansion properties of carbon nanotubes using molecular dynamics simulations

The axial coefficients of thermal expansion (CTE) of various carbon nanotubes (CNTs), i.e., single-wall carbon nanotubes (SWCNTs), and some multi-wall carbon nanotubes (MWCNTs), were predicted using molecular dynamics (MDs) simulations. The effects of two parameters, i.e., temperature and the CNT diameter, on CTE were investigated extensively. For all SWCNTs and MWCNTs, the obtained results clearly revealed that within a wide low temperature range, their axial CTEs are negative. As the diameter of CNTs decreases, this temperature range for negative axial CTEs becomes narrow, and positive axial CTEs appear in high temperature range. It was found that the axial CTEs vary nonlinearly with the temperature, however, they decrease linearly as the CNT diameter increases. Moreover, within a wide temperature range, a set of empirical formulations was proposed for evaluating the axial CTEs of armchair and zigzag SWCNTs using the above two parameters. Finally, it was found that the absolute value of the negative axial CTE of any MWCNT is much smaller than those of its constituent SWCNTs, and the average value of the CTEs of its constituent SWCNTs. The present fundamental study is very important for understanding the thermal behaviors of CNTs in such as nanocomposite temperature sensors, or nanoelectronics devices using CNTs.

Excited-state dynamics in diketopyrrolopyrrole-based copolymer for organic photovoltaics investigated by transient optical spectroscopy

We investigate the photoexcited state dynamics in a donor-acceptor copolymer, poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]- pyrrole-1,4-dione-alt-naphthalene} (pDPP-TNT), by picosecond fluorescence and femtosecond transient absorption spectroscopies. Timeresolved fluorescence lifetime measurements of pDPP-TNT thin films reveal that the lifetime of the singlet excited state is 185 ± 5 ps and that singlet-singlet annihilation occurs at excitation photon densities above 6 × 1017 photons/cm3. From the results of singlet-singlet annihilation analysis, we estimate that the single-singlet annihilation rate constant is (6.0 ± 0.2) × 109cm3 s-1 and the singlet diffusion length is -7 nm. From the comparison of femtosecond transient absorption measurements and picosecond fluorescence measurements, it is found that the time profile of the photobleaching signal in the charge-transfer (CT) absorption band coincides with that of the fluorescence intensity and there is no indication of long-lived species, which clearly suggests that charged species, such as polaron pairs and triplet excitons, are not effectively photogenerated in the neat pDPP-TNT polymer.

Furan substituted diketopyrrolopyrrole and thienylenevinylene based low band gap copolymer for high mobility organic thin film transistors

A novel solution processable donor-acceptor (D-A) based low band gap polymer semiconductor poly{3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4- c]pyrrole-1,4-dione-alt-thienylenevinylene} (PDPPF-TVT), was designed and synthesized by a Pd-catalyzed Stille coupling route. An electron deficient furan based diketopyrrolopyrrole (DPP) block and electron rich thienylenevinylene (TVT) donor moiety were attached alternately in the polymer backbone. The polymer exhibited good solubility, film forming ability and thermal stability. The polymer exhibits wide absorption bands from 400 nm to 950 nm (UV-vis-NIR region) with absorption maximum centered at 782 nm in thin film. The optical band gap (Eoptg) calculated from the polymer film absorption onset is around 1.37 eV. The π-energy band level (ionization potential) calculated by photoelectron spectroscopy in air (PESA) for PDPPF-TVT is around 5.22 eV. AFM and TEM analyses of the polymer reveal nodular terrace morphology with optimized crystallinity after 200 °C thermal annealing. This polymer exhibits p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices. The highest hole mobility of 0.13 cm 2 V -1 s -1 is achieved in bottom gate and top-contact OTFT devices with on/off ratios in the range of 10 6-10 7. This work reveals that the replacement of thiophene by furan in DPP copolymers exhibits such a high mobility, which makes DPP furan a promising block for making a wide range of promising polymer semiconductors for broad applications in organic electronics.

Iron(II) spin-transition complexes with dendritic ligands, part II

The dendritic triazole-based complexes \[Fe(G1-BOC)3](triflate) 2·xH2O (1; G1-BOC = tert-butyl {3-\[3-(3-tert- butoxycarbonylaminopropyl)-5-(\[1,2,4]triazol-4-ylcarbamoyl)-phenyl]propyl} carbamate, triflate = CF3SO3-), \[Fe(G1-BOC) 3]-(tosylate)2·xH2O(2;tosylate = p-CH3PhSO3-),\[Fe(G1-DPBE)3]-(triflate) 2·xH2O {3; G1-DPBE = 3,5-bis(3,5- didodecaoxybenzyloxy)-N-\[1,2,4]triazol-4-ylbenzamide}, \[Fe(G1-DPBE) 3]-(tosylate)2·xH2O (4) and \[Fe(G1-DPBE)3](BF4)2·xH2O (5) were designed and synthesized. Magnetic and thermal properties of these novel complexes were characterized by magnetic susceptibility measurements, 57Fe Mössbauer spectroscopy and thermogravimetric analysis or differential scanning calorimetry, respectively. All dendritic complexes under study show different spin-transition behaviour with respect to the nature of different dendritic ligands and counteranions. Complexes 1 and 2 have pronounced effects of a spin-state change during the first heating process and gradual spintransition properties for further temperature treatments, whereas 3 and 4 exhibited a very sharp spin-state change in the first heating procedures. Complex 5 showed a gradual spin-transition curve. In this paper, we report how the magnetic properties of these complexes are correlated with noncoordinated water molecules and their effects on spin states.

Wearable neuroimaging and emotion : investigating emotional responses to architectural environments with functional near-infrared spectroscopy (fNIRS)

Supported by contemporary theories of architectural aesthetics and neuro-aesthetics this paper presents a case for the use of portable fNIRS imaging in the assessment of emotional responses to spatial environments experienced by both blind and sighted. The aim of the paper is to outline the implications of fNIRS for spatial research and practice within the field of architecture, thereby suggesting a potential taxonomy of particular formations of space and affect. Empirical neurological study of affect and spatial experience from an architectural design perspective remains in many instances unchartered. Clinical research using the portable non-invasive neuro-imaging device, functional near infrared spectroscopy (fNIRS) is proving convincing in its ability to detect emotional responses to visual, spatio-auditory and task based stimuli, providing a firm basis to potentially track cortical activity in the appraisal of architectural environments. Additionally, recent neurological studies have sought to explore the manifold sensory abilities of the visually impaired to better understand spatial perception in general. Key studies reveal that early blind participants perform as well as sighted due to higher auditory and somato-sensory spatial acuity. For instance, face vision enables the visually impaired to detect environments through skin pressure, enabling at times an instantaneous impression of the layout of an unfamiliar environment. Studies also report pleasant and unpleasant emotional responses such as ‘weightedness’ or ‘claustrophobia’ within certain interior environments, revealing a deeper perceptual sensitivity then would be expected. We conclude with justification that comparative fNIRS studies between the sighted and blind concerning spatial experience have the potential to provide greater understanding of emotional responses to architectural environments.