Cadmium-free quantum dots in aqueous solution: potential for fingermark detection, synthesis and an application to the detection of fingermarks in blood on non-porous surfaces

The use of quantum dots (QDs) in the area of fingermark detection is currently receiving a lot of attention in the forensic literature. Most of the research efforts have been devoted to cadmium telluride (CdTe) quantum dots often applied as powders to the surfaces of interests. Both the use of cadmium and the nano size of these particles raise important issues in terms of health and safety. This paper proposes to replace CdTe QDs by zinc sulphide QDs doped with copper (ZnS:Cu) to address these issues. Zinc sulphide-copper doped QDs were successfully synthesized, characterized in terms of size and optical properties and optimized to be applied for the detection of impressions left in blood, where CdTe QDs proved to be efficient. Effectiveness of detection was assessed in comparison with CdTe QDs and Acid Yellow 7 (AY7, an effective blood reagent), using two series of depletive blood fingermarks from four donors prepared on four non-porous substrates, i.e. glass, transparent polypropylene, black polyethylene and aluminium foil. The marks were cut in half and processed separately with both reagents, leading to two comparison series (ZnS:Cu vs. CdTe, and ZnS:Cu vs. AY7). ZnS:Cu proved to be better than AY7 and at least as efficient as CdTe on most substrates. Consequently, copper-doped ZnS QDs constitute a valid substitute for cadmium-based QDs to detect blood marks on non-porous substrates and offer a safer alternative for routine use.

Metal surface and subsurface inspection using nondestructive optical methods

This thesis considers nondestructive optical methods for metal surface and subsurface inspection. The main purpose of this thesis was to study some optical methods in order to find out their applicability to industrial measurements. In laboratory testing the simplest light scattering approach, measurement of specular reflectance, was used for surface roughness evaluation. Surface roughness, curvature and finishing process of metal sheets were determined by specular reflectance measurements. Using a fixed angleof incidence, the specular reflectance method might be automated for industrialinspection. For defect detection holographic interferometry and thermography were compared. Using either holographic interferometry or thermography, relativelysmall-size defects in metal plates could be revealed. Holographic techniques have some limitations for industrial measurements. On the contrary, thermography has excellent prospects for on-line inspection, especially with scanning techniques.

Using the optical mouse sensor as a two-euro counterfeit coin detector

In this paper, the sensor of an optical mouse is presented as a counterfeit coin detector applied to the two-Euro case. The detection process is based on the short distance image acquisition capabilities of the optical mouse sensor where partial images of the coin under analysis are compared with some partial reference coin images for matching. Results show that, using only the vision sense, the counterfeit acceptance and rejection rates are very similar to those of a trained user and better than those of an untrained user.

Development of phase retrieval algorithm and techniques for optical spectrum analysis

Coherent anti-Stokes Raman scattering is the powerful method of laser spectroscopy in which significant successes are achieved. However, the non-linear nature of CARS complicates the analysis of the received spectra. The objective of this Thesis is to develop a new phase retrieval algorithm for CARS. It utilizes the maximum entropy method and the new wavelet approach for spectroscopic background correction of a phase function. The method was developed to be easily automated and used on a large number of spectra of different substances.. The algorithm was successfully tested on experimental data.

Hardcopy quality parameters to ensure structures detection at digital mammography

Objective To develop procedures to ensure consistency of printing quality of digital images, by means of hardcopy quantitative analysis based on a standard image. Materials and Methods Characteristics of mammography DI-ML and general purpose DI-HL films were studied through the QC-Test utilizing different processing techniques in a FujiFilm®-DryPix4000 printer. A software was developed for sensitometric evaluation, generating a digital image including a gray scale and a bar pattern to evaluate contrast and spatial resolution. Results Mammography films showed maximum optical density of 4.11 and general purpose films, 3.22. The digital image was developed with a 33-step wedge scale and a high-contrast bar pattern (1 to 30 lp/cm) for spatial resolution evaluation. Conclusion Mammographic films presented higher values for maximum optical density and contrast resolution as compared with general purpose films. The utilized digital processing technique could only change the image pixels matrix values and did not affect the printing standard. The proposed digital image standard allows greater control of the relationship between pixels values and optical density obtained in the analysis of films quality and printing systems.

Use of the Optical Cantilever Microphone in Photoacoustic Spectroscopy

A novel cantilever pressure sensor was developed in the Department of Physics at the University of Turku in order to solve the sensitivity problems which are encountered when condenser microphones are used in photoacoustic spectroscopy. The cantilever pressure sensor, combined with a laser interferometer for the measurement of the cantilever movements, proved to be highly sensitive. The original aim of this work was to integrate the sensor in a photoacoustic gas detector working in a differential measurement scheme. The integration was made successfully into three prototypes. In addition, the cantilever was also integrated in the photoacoustic FTIR measurement schemes of gas-, liquid-, and solid-phase samples. A theoretical model for the signal generation in each measurement scheme was created and the optimal celldesign discussed. The sensitivity and selectivity of the differential method were evaluated when a blackbody radiator and a mechanical chopper were used with CO₂, CH4, CO, and C2H4 gases. The detection limits were in the sub-ppm level for all four gases with only a 1.3 second integration time and the cross interference was well below one percent for all gas combinations other than those between hydrocarbons. Sensitivity with other infrared sources was compared using ethylene as an example gas. In the comparison of sensitivity with different infrared sources the electrically modulated blackbody radiator gave a 35 times higher and the CO2-laser a 100 times lower detection limit than the blackbody radiator with a mechanical chopper. As a conclusion, the differential system is well suited to rapid single gas measurements. Gas-phase photoacoustic FTIR spectroscopy gives the best performance, when several components have to be analyzed simultaneously from multicomponent samples. Multicomponent measurements were demonstrated with a sample that contained different concentrations of CO₂, H₂O, CO, and four different hydrocarbons. It required an approximately 10 times longer measurement time to achieve the same detection limit for a single gas as with the differential system. The properties of the photoacoustic FTIR spectroscopy were also compared to conventional transmission FTIR spectroscopy by simulations. Solid- and liquid-phase photoacoustic FTIR spectroscopy has several advantages compared to other techniques and therefore it also has a great variety of applications. A comparison of the signal-to-noise ratio between photoacoustic cells with a cantilever microphone and a condenser microphone was done with standard carbon black, polyethene, and sunflower oil samples. The cell with the cantilever microphone proved to have a 5-10 times higher signal-to-noise ratio than the reference detector, depending on the sample. Cantilever enhanced photoacoustics will be an effective tool for gas detection and analysis of solid- and liquid-phase samples. The preliminary prototypes gave good results in all three measurement schemes that were studied. According to simulations, there are possibilities for further enhancement of the sensitivity, as well as other properties, of each system.

Photometric and Halpha observations of LSI+61·303: detection of a 26 day V and JHK band modulation

We present new optical and infrared photometric observations and high resolution H α spectra of the periodic radio star LSI+61◦303. The optical photometric data set covers the time interval 1985-1993 and amounts to about a hundred nights. A period of ∼26 days is found in the V band. The infrared data also present evidence for a similar periodicity, but with higher amplitude of variation ((0.m 2). The spectroscopic observations include 16 intermediate and high dispersion spectra of LSI+61◦303 collected between January 1989 and February 1993. The H α emission line profile and its variations are analyzed. Several emission line parameters -- among them the H α EW and the width of the H α red hump -- change strongly at or close to radio maximum, and may exhibit periodic variability. We also observe a significant change in the peak separation. The H α profile of LSI+61◦303 does not seem peculiar for a Be star. However, several of the observed variations of the H α profile can probably be associated with the presence of the compact, secondary star.

A novel method for fast enrichment and monitoring of hexavalent and trivalent chromium at the ppt level with modified silica MCM-41 and its determination by inductively coupled plasma optical emission spectrometry

Chromium(III) at the ng L-1 level was extracted using partially silylated MCM-41 modified by a tetraazamacrocyclic compound (TAMC) and determined by inductively coupled plasma optical emision spectrometry (ICP OES). The extraction time and efficiency, pH and flow rate, type and minimum amount of stripping acid, and break- through volume were investigated. The method's enrichment factor and detection limit are 300 and 45.5 pg mL-1, respectively. The maximum capacity of the 10 mg of modified silylated MCM-41 was found to be 400.5±4.7 µg for Cr(III). The method was applied to the determination of Cr(III) and Cr(VI) in the wastewater of the chromium electroplating industry and in environmental and biological samples (black tea, hot and black pepper).

Inorganic Nanoparticles and the Immune System: Detection, Selective Activation and Tolerance

The immune system is the responsible for body integrity and prevention of external invasion. On one side, nanoparticles are no triggers that the immune system is prepared to detect, on the other side it is known that foreign bodies, not only bacteria, viruses and parasites, but also inorganic matter, can cause various pathologies such as silicosis, asbestosis or inflammatory reactions. Therefore, nanoparticles entering the body, after interaction with proteins, will be either recognized as self-agents or detected by the immune system, encompassing immunostimulation or immunosuppression responses. The nature of these interactions seems to be dictated not specially by the composition of the material but by modifications of NP coating (composition, surface charge and structure). Herein, we explore the use of gold nanoparticles as substrates to carry multifunctional ligands to manipulate the immune system in a controlled manner, from undetection to immunostimulation. Murine bone marrow macrophages can be activated with artificial nanometric objects consisting of a gold nanoparticle functionalized with peptides. In the presence of some conjugates, macrophage proliferation was stopped and pro-inflammatory cytokines were induced. The biochemical type of response depended on the type of conjugated peptide and was correlated with the degree of ordering in the peptide coating. These findings help to illustrate the basic requirements involved in medical NP conjugate design to either activate the immune system or hide from it, in order to reach their targets before being removed by phagocytes. Additionally, it opens up the possibility to modulate the immune response in order to suppress unwanted responses resulting from autoimmunity, or allergy or to stimulate protective responses against pathogens.

Development of an optical redox chemical sensor for nitrite determination

An optical chemical sensor for the determination of nitrite based on incorporating methyltrioctylammonium chloride as an anionic exchanger on the triacetylcellulose polymer has been reported. The response of the sensor is based on the redox reaction between nitrite in aqueous solution and iodide adsorbed on sensing membrane using anion exchange phenomena. The sensing membrane reversibly responses to nitrite ion over the range of 6.52×10-6 - 8.70×10-5 mol L-1 with a detection limit of 6.05×10-7 mol L-1 (0.03 µg mL-1) and response time of 6 min. The relative standard deviation for eight replicate measurements of 8.70×10-6 and 4.34×10-5 mol L-1 of nitrite was 4.4 and 2.5 %, respectively. The sensor was successfully applied for determination of nitrite in food, saliva and water samples.

The use of enzyme-linked immunosorbent assay and immunoblotting for the detection of Campylobacter fetus immunoglobulins in the cervico-vaginal mucus of female cattle

An indirect enzyme-linked immunosorbent assay was developed to detect antigen-specific secretory IgA antibodies to Campylobacter fetus subsp. venerealis in bovine vaginal mucus with a protein extract of the Campylobacter fetus subsp. venerealis by the acid glycine extraction method. Mean optical density measurement (λ=450 nm) was 0.143±0.9. The most immunoreactive protein bands of the Campylobacter fetus subsp. venerealis or Campylobacter fetus subsp. fetus recognized by IgA in immunoblotting, using bovine vaginal mucus samples, migrate at 42.6 kDa. The protein that migrates at 93 kDa was recognized exclusively for C. fetus subsp. venerealis. A positive vaginal mucus sample of a cow from negative herd recognized antigens of C. jejuni subsp. jejuni e C. fetus subsp. fetus.

Linear prediction in optical spectroscopy

A linear prediction procedure is one of the approved numerical methods of signal processing. In the field of optical spectroscopy it is used mainly for extrapolation known parts of an optical signal in order to obtain a longer one or deduce missing signal samples. The first is needed particularly when narrowing spectral lines for the purpose of spectral information extraction. In the present paper the coherent anti-Stokes Raman scattering (CARS) spectra were under investigation. The spectra were significantly distorted by the presence of nonlinear nonresonant background. In addition, line shapes were far from Gaussian/Lorentz profiles. To overcome these disadvantages the maximum entropy method (MEM) for phase spectrum retrieval was used. The obtained broad MEM spectra were further underwent the linear prediction analysis in order to be narrowed.

Photon Upconverting Nanophosphors: Unique Reporters for Optical Biosensing

Upconversion photoluminescence is a unique property of mostly certain inorganic materials, which are capable of converting low-energy infrared radiation into a higher-energy emission at visible wavelengths. This anti-Stokes shift enables luminescence detection without autofluorescence, which makes the upconverting materials a highly suitable reporter technology for optical biosensing applications. Furthermore, they exhibit long luminescence lifetime with narrow bandwidths also at the optical window of biomaterials enabling luminescence measurements in challenging sample matrices, such as whole blood. The aim of this thesis was to study the unique properties and the applicability of nano-sized upconverting phosphors (UCNPs) as reporters in biosensing applications. To render the inorganic nanophosphors water-dispersible and biocompatible, they were subjected to a series of surface modifications starting with silica-encapsulation and ending with a bioconjugation step with an analyte-recognizing biomolecule. The paramagnetism of the lanthanide dopants in the nanophosphors was exploited to develop a highly selective separation method for the UCNP-bioconjugates based on the magnetic selectivity of the high gradient magnetic separation (HGMS) system. The applicability of the nano-sized UCNPs as reporters in challenging sample matrices was demonstrated in two homogeneous sensing applications based on upconversion resonance energy transfer (UC-RET). A chemosensor for intracellular pH was developed exploiting UC-RET between the UCNP and a fluorogenic pH-sensitive dye with strongly increasing fluorescence intensity in decreasing pH. The pH-independent emission of the UCNPs at 550 nm was used for referencing. The applicability of the pH-nanosensor for intracellular pH measurement was tested in HeLa cells, and the acidic pH of endosomes could be detected with a confocal fluorescence microscope. Furthermore, a competitive UC-RET-based assay for red blood cell folic acid was developed for the measurement of folate directly from a whole blood sample. The optically transparent window of biomaterials was used in both the excitation and the measurement of the UC-RET sensitized emission of a near-infrared acceptor dye to minimize sample absorption, and the anti-Stokes detection completely eliminated the Stokes-shifted autofluorescence. The upconversion photoluminescence efficiency is known to be dependent on crystallite size, because the increasing surface-to-volume ratio of nano-sized UCNPs renders them more susceptible to quenching effects of the environment than their bulk counterpart. Water is known to efficiently quench the luminescence of lanthanide dopants. In this thesis, the quenching mechanism of water was studied using luminescence decay measurements. Water was found to quench the luminescence of UCNPs by increasing the non-radiative relaxation of the excited state of Yb3+ sensitizer ion, which had a very strong quenching effect on upconversion luminescence intensity.

Developing correlative Optical-Photoacustic microscopy for high-resolution in vivo imaging

PhotoAcoustic Imaging (PAI) is a branch in clinical and pre-clinical imaging, that refers to the techniques mapping acoustic signals caused by the absorption of the short laser pulse. This conversion of electromagnetic energy of the light to the mechanical (acoustic) energy is usually called photoacoustic effect. PAI, by combining optical excitation with acoustical detection, is able to preserve the diffraction limited spatial resolution. At the same time, the penetration depth is extended beyond the diffusive limit. The Laser-Scanning PhotoAcoustic Microscope system (LS-PAM) has been developed, that offers the axial resolution of 7.75 µm with the lateral resolution better than 10 µm. The first in vivo imaging experiments were carried out. Thus, in vivo label-free imaging of the mouse ear was performed. The principle possibility to image vessels located in deep layers of the mouse skin was shown. As well as that, a gold printing sample, vasculature of the Chick Chorioallantoic Membrane Assay, Drosophila larvae were imaged by PAI. During the experimental work, a totally new application of PAM was found, in which the acoustic waves, generated by incident light can be used for further imaging of another sample. In order to enhance the performance of the presented system two main recommendation can be offered. First, the current system should be transformed into reflection-mode setup system. Second, a more powerful source of light with the sufficient repetition rate should be introduced into the system.

The infared optical properties of Sr2RuO4 and SmTiO3 including an object-oriented resistivity interface /

The perovskite crystal structure is host to many different materials from insulating to superconducting providing a diverse range of intrinsic character and complexity. A better fundamental description of these materials in terms of their electronic, optical and magnetic properties undoubtedly precedes an effective realization of their application potential. SmTiOa, a distorted perovskite has a strongly localized electronic structure and undergoes an antiferromagnetic transition at 50 K in its nominally stoichiometric form. Sr2Ru04 is a layered perovskite superconductor (ie. Tc % 1 K) bearing the same structure as the high-tem|>erature superconductor La2_xSrrCu04. Polarized reflectance measurements were carried out on both of these materials revealing several interesting features in the far-infrared range of the spectrum. In the case of SmTiOa, although insulating, evidence indicates the presence of a finite background optical conductivity. As the temperature is lowered through the ordering temperature a resonance feature appears to narrow and strengthen near 120 cm~^ A nearby phonon mode appears to also couple to this magnetic transition as revealed by a growing asymmetry in the optica] conductivity. Experiments on a doped sample with a greater itinerant character and lower Neel temperature = 40 K also indicate the presence of this strongly temperature dependent mode even at twice the ordering temperature. Although the mode appears to be sensitive to the magnetic transition it is unclear whether a magnon assignment is appropriate. At very least, evidence suggests an interesting interaction between magnetic and electronic excitations. Although Sr2Ru04 is highly anisotropic it is metallic in three-dimensions at low temperatures and reveals its coherent transport in an inter-plane Drude-like component to the highest temperatures measured (ie. 90 K). An extended Drude analysis is used to probe the frequency dependent scattering character revealing a peak in both the mass enhancement and scattering rate near 80 cm~* and 100 cm~* respectively. All of these experimental observations appear relatively consistent with a Fermi-liquid picture of charge transport. To supplement the optical measurements a resistivity station was set up with an event driven object oriented user interface. The program controls a Keithley Current Source, HP Nano-Voltmeter and Switching Unit as well as a LakeShore Temperature Controller in order to obtain a plot of the Resistivity as a function of temperature. The system allows for resistivity measurements ranging from 4 K to 290 K using an external probe or between 0.4 K to 295 K using a Helium - 3 Cryostat. Several materials of known resistivity have confirmed the system to be robust and capable of measuring metallic samples distinguishing features of several fiQ-cm.