Printed platforms for paper-based analytical applications

Paper-based analytical technologies enable quantitative and rapid analysis of analytes from various application areas including healthcare, environmental monitoring and food safety. Because paper is a planar, flexible and light weight substrate, the devices can be transported and disposed easily. Diagnostic devices are especially valuable in resourcelimited environments where diagnosis as well as monitoring of therapy can be made even without electricity by using e.g. colorimetric assays. On the other hand, platforms including printed electrodes can be coupled with hand-held readers. They enable electrochemical detection with improved reliability, sensitivity and selectivity compared with colorimetric assays. In this thesis, different roll-to-roll compatible printing technologies were utilized for the fabrication of low-cost paper-based sensor platforms. The platforms intended for colorimetric assays and microfluidics were fabricated by patterning the paper substrates with hydrophobic vinyl substituted polydimethylsiloxane (PDMS) -based ink. Depending on the barrier properties of the substrate, the ink either penetrates into the paper structure creating e.g. microfluidic channel structures or remains on the surface creating a 2D analog of a microplate. The printed PDMS can be cured by a roll-ro-roll compatible infrared (IR) sintering method. The performance of these platforms was studied by printing glucose oxidase-based ink on the PDMS-free reaction areas. The subsequent application of the glucose analyte changed the colour of the white reaction area to purple with the colour density and intensity depending on the concentration of the glucose solution. Printed electrochemical cell platforms were fabricated on paper substrates with appropriate barrier properties by inkjet-printing metal nanoparticle based inks and by IR sintering them into conducting electrodes. Printed PDMS arrays were used for directing the liquid analyte onto the predetermined spots on the electrodes. Various electrochemical measurements were carried out both with the bare electrodes and electrodes functionalized with e.g. self assembled monolayers. Electrochemical glucose sensor was selected as a proof-of-concept device to demonstrate the potential of the printed electronic platforms.

New families of highly efficient, halogen-free flame retardants for polypropylene (PP)

The driving forces for current research of flame retardants are increased fire safety in combination with flame retardant formulations that fulfill the criteria of sustainable production and products. In recent years, important questions about the environmental safety of antimony, and in particular, brominated flame retardants have been raised. As a consequence of this, the current doctoral thesis work describes efforts to develop new halogen-free flame retardants that are based on various radical generators and phosphorous compounds. The investigation was first focused on compounds that are capable of generating alkyl radicals in order to study their role on flame retardancy of polypropylene. The family of azoalkanes was selected as the cleanest and most convenient source of free alkyl radicals. Therefore, a number of symmetrical and unsymmetrical azoalkanes of the general formula R-N=N-R’ were prepared. The experimental results show that in the series of different sized azocycloalkanes the flame retardant efficacy decreased in the following order: R = R´= cyclohexyl > cyclopentyl > cyclobutyl > cyclooctanyl > cyclododecanyl. However, in the series of aliphatic azoalkanes compounds, the efficacy decreased as followed: R = R´= n-alkyl > tert-butyl > tert-octyl. The most striking difference in flame retardant efficacy was observed in thick polypropylene plaques of 1 mm, e.g. azocyclohexane (AZO) had a much better flame retardant performance than did the commercial reference FR (Flamestab® NOR116) in thick PP sections. In addition, some of the prepared azoalkane flame retardants e.g. 4’4- bis(cyclohexylazocyclohexyl) methane (BISAZO) exhibited non-burning dripping behavior. Extrusion coating experiments of flame retarded low density polyethylene (LDPE) onto a standard machine finished Kraft paper were carried out in order to investigate the potential of azoalkanes in multilayer facings. The results show that azocyclohexane (AZO) and 4’4-bis (cyclohexylazocyclohexyl) methane (BISAZO) can significantly improve the flame retardant properties of low density polyethylene coated paper already at 0.5 wt.% loadings, provided that the maximum extrusion temperature of 260 oC is not exceeded and coating weight is kept low at 13 g/m2. In addition, various triazene-based flame retardants (RN1=N2-N3R’R’’) were prepared. For example, polypropylene samples containing a very low concentration of only 0.5 wt.% of bis- 4’4’-(3’3’-dimethyltriazene) diphenyl ether and other triazenes passed the DIN 4102-1 test with B2 classification. It is noteworthy that no burning dripping could be detected and the average burning times were very short with exceptionally low weight losses. Therefore, triazene compounds constitute a new and interesting family of radical generators for flame retarding of polymeric materials. The high flame retardant potential of triazenes can be attributed to their ability to generate various types of radicals during their thermal decomposition. According to thermogravimetric analysis/Fourier transform infrared spectroscopy/MS analysis, triazene units are homolytically cleaved into various aminyl, resonance-stabilized aryl radicals, and different CH fragments with simultaneous evolution of elemental nitrogen. Furthermore, the potential of thirteen aliphatic, aromatic, thiuram and heterocyclic substituted organic disulfide derivatives of the general formula R-S-S-R’ as a new group of halogen-free flame retardants for polypropylene films have been investigated. According to the DIN 4102- 1 standard ignitibility test, for the first time it has been demonstrated that many of the disulfides alone can effectively provide flame retardancy and self-extinguishing properties to polypropylene films at already very low concentrations of 0.5 wt.%. For the disulfide family, the highest FR activity was recorded for 5’5’-dithiobis (2-nitrobenzoic acid). Very low values for burning length (53 mm) and burning time (10 s) reflect significantly increased fire retardant performance of this disulfide compared to other compounds in this series as well as to Flamestab® NOR116. Finally, two new, phosphorus-based flame retardants were synthesized: P’P-diphenyl phosphinic hydrazide (PAH) and melamine phenyl phosphonate (MPhP). The DIN 4102-1 test and the more stringent UL94 vertical burning test (UL94 V) were used to assess the formulations ability to extinguish a flame once ignited. A very strong synergistic effect with azoalkanes was found, i.e. in combination with these radical generators even UL94 V0 rate could be obtained.

Distribution-Free Bounds for Serial Correlation Coefficients in Heteroskedastic Symmetric Time Series

We consider the problem of testing whether the observations X1, ..., Xn of a time series are independent with unspecified (possibly nonidentical) distributions symmetric about a common known median. Various bounds on the distributions of serial correlation coefficients are proposed: exponential bounds, Eaton-type bounds, Chebyshev bounds and Berry-Esséen-Zolotarev bounds. The bounds are exact in finite samples, distribution-free and easy to compute. The performance of the bounds is evaluated and compared with traditional serial dependence tests in a simulation experiment. The procedures proposed are applied to U.S. data on interest rates (commercial paper rate).

Copyright is an Impediment to the Free Flow of Ideas

"Sur un ton humoristique, les auteurs avouent être des voleurs… d’idées. À quoi riment les lois sur le droit d’auteur demandent-ils ? À l’origine, ce ne sont pas les droits des créateurs que le souverain ou l’État voulait protéger, mais bien les privilèges des éditeurs. Et d’où vient qu’on ait ainsi accordé à ces derniers le droit exclusif de publier ? C’est que dès l’invention de l’imprimerie, les hommes de pouvoir ont bien vu la menace que représentait pour eux la dissémination des idées : le calcul qu’ils ont fait a profité aux imprimeurs. Le phénomène n’est pas étranger à l’existence des permis de radiodiffusion / télévision existant de nos jours dans nos États démocratiques ; et l’histoire se répète comme on l’observe aujourd’hui quant à la régulation du réseau Internet. Quand les éditeurs se rendirent compte qu’ils ne pouvaient plus avoir la main haute sur tout ce qui se publiait, ils ont pris prétexte du droit des créateurs pour protéger leurs propres intérêts. Ni l’éthique ni l’esthétique ne motivaient les éditeurs , mais bien leurs seuls intérêts commerciaux, légitimes au demeurant. Deux factions s’opposent aujourd’hui quant à la question du droit des auteurs à l’ère numérique. La vieille garde se bat pour préserver à peu de choses près le statu quo tandis que ses vis-à-vis proclament la mort du droit d’auteur tel qu’il a existé. Et quel modèle nouveau préconisent ces derniers ? En fait, ils ne s’opposent pas à toute forme de protection pour ceux qui traditionnellement en ont bénéficié, mais songent à des mécanismes nouveaux …, de sorte que la vieille garde n’a pas à s’en faire outre mesure. Le fond du problème est ailleurs soutiennent MM. Benyekhlef et Tresvant : même si les avocats plaideront que ce ne sont pas les idées, mais bien la forme particulière qu’un créateur a choisie pour les exprimer qu’on protège par les lois sur le droit d’auteur, cela ne change rien. Dès qu’une idée est exprimée et fixée d’une certaine manière, il devient plus difficile de l’exprimer à nouveau puisqu’une partie du champ virtuel qu’elle pouvait occuper est déjà conquise, à bon droit selon le droit actuel. Il faut en conclure que le droit d’auteur nouveau, comme le droit d’auteur traditionnel, est une entrave à la libre circulation des idées."

Development of an enzyme immobilization platform based on microencapsulation for paper-based biosensors

Un papier bioactif est obtenu par la modification d’un papier en y immobilisant une ou plusieurs biomolécules. La recherche et le développement de papiers bioactifs est en plein essor car le papier est un substrat peu dispendieux qui est déjà d’usage très répandu à travers le monde. Bien que les papiers bioactifs n’aient pas connus de succès commercial depuis la mise en marche de bandelettes mesurant le taux de glucose dans les années cinquante, de nombreux groupes de recherche travaillent à immobiliser des biomolécules sur le papier pour obtenir un papier bioactif qui est abordable et possède une bonne durée de vie. Contrairement à la glucose oxidase, l’enzyme utilisée sur ces bandelettes, la majorité des biomolécules sont très fragiles et perdent leur activité très rapidement lorsqu’immobilisées sur des papiers. Le développement de nouveaux papiers bioactifs pouvant détecter des substances d’intérêt ou même désactiver des pathogènes dépend donc de découverte de nouvelles techniques d’immobilisation des biomolécules permettant de maintenir leur activité tout en étant applicable dans la chaîne de production actuelle des papiers fins. Le but de cette thèse est de développer une technique d’immobilisation efficace et versatile, permettant de protéger l’activité de biomolécules incorporées sur des papiers. La microencapsulation a été choisie comme technique d’immobilisation car elle permet d’enfermer de grandes quantités de biomolécules à l’intérieur d’une sphère poreuse permettant leur protection. Pour cette étude, le polymère poly(éthylènediimine) a été choisi afin de générer la paroi des microcapsules. Les enzymes laccase et glucose oxidase, dont les propriétés sont bien établies, seront utilisées comme biomolécules test. Dans un premier temps, deux procédures d’encapsulation ont été développées puis étudiées. La méthode par émulsion produit des microcapsules de plus petits diamètres que la méthode par encapsulation utilisant un encapsulateur, bien que cette dernière offre une meilleure efficacité d’encapsulation. Par la suite, l’effet de la procédure d’encapsulation sur l’activité enzymatique et la stabilité thermique des enzymes a été étudié à cause de l’importance du maintien de l’activité sur le développement d’une plateforme d’immobilisation. L’effet de la nature du polymère utilisé pour la fabrication des capsules sur la conformation de l’enzyme a été étudié pour la première fois. Finalement, l’applicabilité des microcapsules de poly(éthylèneimine) dans la confection de papiers bioactifs a été démontré par le biais de trois prototypes. Un papier réagissant au glucose a été obtenu en immobilisant des microcapsules contenant l’enzyme glucose oxidase. Un papier sensible à l’enzyme neuraminidase pour la détection de la vaginose bactérienne avec une plus grande stabilité durant l’entreposage a été fait en encapsulant les réactifs colorimétriques dans des capsules de poly(éthylèneimine). L’utilisation de microcapsules pour l’immobilisation d’anticorps a également été étudiée. Les avancées au niveau de la plateforme d’immobilisation de biomolécules par microencapsulation qui ont été réalisées lors de cette thèse permettront de mieux comprendre l’effet des réactifs impliqués dans la procédure de microencapsulation sur la stabilité, l’activité et la conformation des biomolécules. Les résultats obtenus démontrent que la plateforme d’immobilisation développée peut être appliquée pour la confection de nouveaux papiers bioactifs.

Luminescence from Surfactant-Free ZnO Quantum Dots Prepared by Laser Ablation in Liquid

Highly transparent, luminescent and biocompatible ZnO quantum dots were prepared in water, methanol, and ethanol using liquid-phase pulsed laser ablation technique without using any surfactant. Transmission electron microscopy analysis confirmed the formation of good crystalline ZnO quantum dots with a uniform size distribution of 7 nm. The emission wavelength could be varied by varying the native defect chemistry of ZnO quantum dots and the laser fluence. Highly luminescent nontoxic ZnO quantum dots have exciting application potential as florescent probes in biomedical applications.

A Simple Free-Space Method for Measuring the Complex Permittivity of Single and Compound Dielectric Materials

A simple and efficient method for determining the complex permittivity of dielectric materials from both reflected and transmitted signals is presented. It is also novel because the technique is implemented using two pyramidal horns without any focusing mechanisms. The dielectric constant of a noninteractive and distributive (NID) mixture of dielectrics is also determined

Laser emission from transversely pumped dye-doped free-standing polymer film

We present a compact solid-state laser based on leaky mode propagation from a dye-doped polymer free-standing film waveguide. The edge emitted spectrum clearly indicated the existence of periodic resonant modes. The reflections from the lateral faces of the free-standing film provided the optical feedback thus giving rise to a Fabry–Perot like optical cavity. This together with the guidance through the gain medium gave rise to intense narrow emission lines. For a pump energy of 1.82 mJ/pulse, an intense line with FWHM ∼0.4 nmwas observed at 576.5 nm.

Laser emission from transversely pumped dye-doped free-standing polymer film

We present a compact solid-state laser based on leaky mode propagation from a dye-doped polymer free-standing film waveguide. The edge emitted spectrum clearly indicated the existence of periodic resonant modes. The reflections from the lateral faces of the free-standing film provided the optical feedback thus giving rise to a Fabry–Perot like optical cavity. This together with the guidance through the gain medium gave rise to intense narrow emission lines. For a pump energy of 1.82 mJ/pulse, an intense line with FWHM ∼0.4 nmwas observed at 576.5 nm.

Laser emission from transversely pumped dye-doped free-standing polymer film

We present a compact solid-state laser based on leaky mode propagation from a dye-doped polymer free-standing film waveguide. The edge emitted spectrum clearly indicated the existence of periodic resonant modes. The reflections from the lateral faces of the free-standing film provided the optical feedback thus giving rise to a Fabry–Perot like optical cavity. This together with the guidance through the gain medium gave rise to intense narrow emission lines. For a pump energy of 1.82 mJ/pulse, an intense line with FWHM ∼0.4 nmwas observed at 576.5 nm.

Optical absorption studies of free (H2Pc) and rare earth (RePc) phthalocyanine doped borate glasses

Optical absorption studies of free base and rare earth incorporated phthalocyanine doped borate glass matrix are reported for the first lime. The absorption spectra recorded in the UV- VIS region show two well defined absorption bands of phthalocyanine (Pc) molecule, namely the Soret band (B) and the Q band. The Q band always shows its characteristic splitting in all the doped glass matrices and the intensities of these components are found to vary from one Pc to another. Some of the important optical parameters, namely optical absorption coefficient (a), molar extinction coefficient (ε), absorption cross section (σa), oscillator strength (f), electric dipole strength (q2), absorption half bandwidth (Δλ) of the principal optical transitions have also been evaluated. Moreover, the spectral dependence of refractive index (n) and thereby the optical dielectric constant (ε) on wavelength yielded values of carrier concentration to effective mass ratio (N/m*) of the phthalocyanine molecule in the present glassy systems. Optical band gap (Eg) and width of the band tail (Et) are computed and their variations among the prepared samples are also discussed.

Buried-object detection using free-space time-domain near-field measurements

The detection of buried objects using time-domain freespace measurements was carried out in the near field. The location of a hidden object was determined from an analysis of the reflected signal. This method can be extended to detect any number of objects. Measurements were carried out in the X- and Ku-bands using ordinary rectangular pyramidal horn antennas of gain 15 dB. The same antenna was used as the transmitter and recei er. The experimental results were compared with simulated results by applying the two-dimensional finite-difference time-domain(FDTD)method, and agree well with each other. The dispersi e nature of the dielectric medium was considered for the simulation.

A Novel Decision Tree Algorithm for Numeric Datasets - C 4.5*Stat

Decision trees are very powerful tools for classification in data mining tasks that involves different types of attributes. When coming to handling numeric data sets, usually they are converted first to categorical types and then classified using information gain concepts. Information gain is a very popular and useful concept which tells you, whether any benefit occurs after splitting with a given attribute as far as information content is concerned. But this process is computationally intensive for large data sets. Also popular decision tree algorithms like ID3 cannot handle numeric data sets. This paper proposes statistical variance as an alternative to information gain as well as statistical mean to split attributes in completely numerical data sets. The new algorithm has been proved to be competent with respect to its information gain counterpart C4.5 and competent with many existing decision tree algorithms against the standard UCI benchmarking datasets using the ANOVA test in statistics. The specific advantages of this proposed new algorithm are that it avoids the computational overhead of information gain computation for large data sets with many attributes, as well as it avoids the conversion to categorical data from huge numeric data sets which also is a time consuming task. So as a summary, huge numeric datasets can be directly submitted to this algorithm without any attribute mappings or information gain computations. It also blends the two closely related fields statistics and data mining

Prediction of Learning Disabilities in School Age Children using SVM and Decision Tree

This paper highlights the prediction of Learning Disabilities (LD) in school-age children using two classification methods, Support Vector Machine (SVM) and Decision Tree (DT), with an emphasis on applications of data mining. About 10% of children enrolled in school have a learning disability. Learning disability prediction in school age children is a very complicated task because it tends to be identified in elementary school where there is no one sign to be identified. By using any of the two classification methods, SVM and DT, we can easily and accurately predict LD in any child. Also, we can determine the merits and demerits of these two classifiers and the best one can be selected for the use in the relevant field. In this study, Sequential Minimal Optimization (SMO) algorithm is used in performing SVM and J48 algorithm is used in constructing decision trees.

Marine Product Exports of Kerala in the ASEAN India Free Trade Area: Possibilities and Challenges

In the backdrop of issues encountered by the marine product exports from Kerala in the traditional strongholds of the European Union and the United States, there is a need to target newer markets. The ASEAN India Trade in Goods Agreement (TIGA) though proposes to liberalize trade between India and the ASEAN member nations, fails to deliver greater market access for our marine products in the markets of the ASEAN nations. This can be attributed to factors such as the lower prevailing MFN base rate in the ASEAN nations, tariff reduction commitments reciprocated by them being lesser than India’s offers, inclusion of our prominent items of export in the restrictive lists of most of the ASEAN nations etc. Export forecast suggests that this is a market to be reckoned, which in turn stipulates the need to secure greater concessions and preferential treatment for our marine product exports in the ASEAN nations to capitalize on the gains that have been made