Synthesis of nanoporous materials for preconcentration and determination of trace elements by ICP-AES ; Investigation and elimination of the memory effects of mercury, gold, silver and boron in ICP-AES

Nanoporous materials with large surface area and well-ordered pore structure have been synthesized. Thiol groups were grafted on the materials' surface to make heavy metal ion pre-concentration media. The adsorption properties ofthe materials were explored. Mercury, gold and silver can be strongly adsorbed by these materials, even in the presence of alkaline earth metal ion. Though the materials can adsorb other heavy metal ions such as lead and copper, they show differential adsorption ability when several ions are present in solution. The adsorption sequence is: mercury> == silver> copper » lead and cadmium. In the second part of this work, the memory effects of mercury, gold, silver and boron were investigated. The addition of 2% L-cysteine and 1% thiourea eliminates the problems of the three metal ions completely. The wash-out time for mercury dropped from more than 20 minutes to 18 seconds, and the wash-out time for gold decreased from more than 30 minutes to 49 seconds. The memory effect of boron can be reduced by the use of mannitol.

Photograph - Dorothy Rungeling and Governor-General's Silver Cup, 1953

A photograph of Dorothy Rungeling with the Silver Cup, the caption reads "Dorothy Rungeling, Canadian woman flier, holds Governor-General's Silver Cup, which she won, as well as a cheque for $500 for winning the Governor-General's Race at the National Air Show held in Toronto last September."

Photograph - Margaret Julia Woodruff Band in a Wedding Dress, in Silver Frame

Black and white photograph, 12 cm x 9 cm, of Margaret Julia Woodruff Band in a seated position, wearing a wedding dress and veil. The photo was taken by Dudley Hoyt of New York. The photo is encased within an ornate, silver frame which is engraved with the initials “M.J.W.”.

Silver Jubilee Hinged Tin from Cadbury

A box commemorating King George V's silver jubilee in 1935.

Silver Pocket Knife

A silver pocket knife with the initials W.K.C. [William Knapp Cleveland]. The knife measures 15 cm in length when opened and 8 1/2 cm in length when closed. There is no silver mark on the knife, but the word "coin" is printed on the blade.

The Bootstrap of Mean for Dependent Heterogeneous Arrays.

Presently, conditions ensuring the validity of bootstrap methods for the sample mean of (possibly heterogeneous) near epoch dependent (NED) functions of mixing processes are unknown. Here we establish the validity of the bootstrap in this context, extending the applicability of bootstrap methods to a class of processes broadly relevant for applications in economics and finance. Our results apply to two block bootstrap methods: the moving blocks bootstrap of Künsch ( 989) and Liu and Singh ( 992), and the stationary bootstrap of Politis and Romano ( 994). In particular, the consistency of the bootstrap variance estimator for the sample mean is shown to be robust against heteroskedasticity and dependence of unknown form. The first order asymptotic validity of the bootstrap approximation to the actual distribution of the sample mean is also established in this heterogeneous NED context.

Intramolecular Direct Functionalization of Cyclopropanes via Silver-Mediated, Palladium Catalysis

Au cours de la dernière décennie, le domaine de la fonctionnalisation directe des liens C–H a connu un intérêt croissant, en raison de la demande de processus chimiques moins dispendieux, plus efficaces et plus écologiques. . Les cyclopropanes représentent un motif structural souvent retrouvé dans des agents biologiquement actifs importants et dans des intermédiaires de synthèse permettant l'accès à des architectures complexes. Malgré leur valeur intrinsèque, la fonctionnalisation directe des cyclopropanes n’a pas été largement explorée. Ce mémoire traitera de deux méthodologies liées, mais tout aussi différentes, impliquant la fonctionnalisation directe des liens C–H cyclopropaniques impliquant des réactions intramoléculaires catalysées par un complex de palladium et assistées par l’argent. Le premier chapitre présentera d’abord un bref survol de la littérature sur les fondements de la fonctionnalisation directe ainsi que les contributions majeures réalisées dans ce domaine. L’accent sera notamment mis sur la fonctionnalisation des centres sp3 et sera souligné par des exemples pertinents. Les découvertes clés concernant le mécanisme et les cycles catalytiques de ces processus seront discutées. Le second chapitre décrira comment les 2-bromoanilides peuvent être utilisés pour accéder à des motifs particuliers de type spiro 3,3’ oxindoles cyclopropyliques. L'optimisation et l’étendue de la réaction seront abordés, suivis par des études mécanistiques réfutant l’hypothèse de la formation d’un intermédiaire palladium-énolate. Ces études mécanistiques comprennent une étude cinétique de l'effet isotopique ainsi que des études sur épimérisation; celles-ci ont confirmé que la réaction se produit par arylation directe. Sur la base des résultats obtenus dans le deuxième chapitre, nous aborderons ensuite la fonctionnalisation directe des benzamides cyclopropyliques lesquels, après une ouverture de cycle, donneront de nouveaux produits benzo [c] azépine-1-ones (chapitre trois). Après avoir présenté une brève optimisation et l’étendue de la réaction, nous discuterons des études mécanistiques impliquées à déduire l'ordre des événements dans le cycle catalytique et à déterminer le rôle des réactifs. Celles-ci permetteront de conclure que la fonctionnalisation de l’unité cyclopropyle se produit avant l’ouverture de cycle et que l'acétate est responsable de la déprotonation-métalation concertée. Le dernier chapitre (chapitre quatre) traitera en rétrospective de ce qui a été appris à partir de deux méthodologies divergentes et connexes et de comment ces résultats peuvent être exploités pour explorer d’autres types de fonctionnalisations directes sur des cyclopropanes.

Investigations on Ultrasonic Transducer Array Systems for NDE of Underwater Pipelines

The main objective of carrying out this investigation is to develop suitable transducer array systems so that underwater pipeline inspection could be carried out in a much better way, a focused beam and electronic steering can reduce inspection time as well. Better results are obtained by optimizing the array parameters. The spacing between the elements is assumed to be half the wavelength so that the interelement interaction is minimum. For NDT applications these arrays are operated at MHz range. The wavelengths become very small in these frequency ranges. Then the size of the array elements becomes very small, requiring hybrid construction techniques for their fabrication. Transducer elements have been fabricated using PVDF as the active, mild steel as the backing and conducting silver preparation as the bonding materials. The transducer is operated in the (3,3) mode. The construction of a high frequency array is comparatively complicated. The interelement spacing between the transducer elements becomes considerably small when high frequencies are considered. It becomes very difficult to construct the transducer manually. The electrode connections to the elements can produce significant loading effect. The array has to be fabricated using hybrid construction techniques. The active materials has to be deposited on a proper substrate and etching techniques are required to fabricate the array. The annular ring, annular cylindrical or other similar structural forms of arrays may also find applications in the near future in treatments were curved contours of the human body are affected.

Polarisation agile active microstrip patch arrays

Two three-clement polarisation-agile active microstrip patch arrays have been developed . The radiating elements are square patches each with two transistors mounted on adjacent edges. The patches radiate orthogonal modes , the relative phase of which can be varied. Radiation patterns show good agreement with predictions from theory, in both linear and circular polarization, and no grating lobes were observed

Thermal diffusivity of rhodamine 6G incorporated in silver nanofluid measured using mode-matched thermal lens technique

Dual beam mode-matched thermal lens method has been employed to measure the heat diffusion in nanofluid of silver with various volumes of rhodamine 6G, both dispersed in water. The important observation is an indication of temperature dependent diffusivity and that the overall heat diffusion is slower in the chemically prepared Ag sol compared to that of water. The experimental results can be explained assuming that Brownian motion is the main mechanism of heat transfer under the present experimental conditions. Light induced aggregation of the nanoparticles can also result in an anomalous diffusion behavior.

Three Component Mannich Reaction and 1,5-Benzodiazepine Synthesis Catalyzed by a Tetranitrile-Silver Complex

This manuscript describes the first example of silver ion complex of a dendritic tetranitrile ligand catalyzed one-pot three component Mannich reaction and 1,5-benzodiazepine synthesis. The catalyst can be separated from the products by a change in the solvent. The catalyst is reusable.

Design Considerations of Sonar Projector Arrays with Improved Performance

Systems which employ underwater acoustic energy for observation or communication are called sonar systems. The active and passive sonars are the two types of systems used for the detection and localisation of targets in underwater. Active sonar involves the transmission of an acoustic signal which, when reflected from a target, provides the sonar receiver with a basis for the detection and estimation. Passive sonar bases its detection and estimation on sounds which emanate from the target itself--Machinery noise, flow noise, transmission from its own active sonar etc.Electroacoustic transducers are used in sonar systems for the transmission and detection of acoustic energy. The transducer which is used for the transmission of acoustic energy is called projector and the one used for reception is called hydrophone. Since a single transducer is not sufficient enough for long range and directional transmission, a properly distributed array of transducers are to be used [9-11].The need and requirement for spatial processing to generate the most favourable directivity patterns for transducer systems used in underwater applications have already been analysed by several investigators [12-21].The desired directivity pattern can be either generated by the use of suitable focussing techniques or by an array of non-directional sensor elements, whose arrangements, spacing and the mode of excitation provide the required radiation pattern or by the combination of these.While computing that the directivity pattern, it is assumed strength of the elements are unaffected by the the source acoustic pressure at each source. However, in closely packed a r r a y s , the acoustic interaction effects experienced among the elements will modify the behaviour of individual elements and in turn will reduce the acoust ic source leve 1 wi t h respect to the maximum t heoret i cal va 1ue a s well as degrade the beam pa t tern. Th i s ef fect shou 1d be reduced in systems that are intended to generate high acoustic power output and unperturbed beam patterns [2,22-31].The work herein presented includes an approach for designing efficient and well behaved underwater transd~cer arrays, taking into account the acoustic interaction effect experienced among the closely packed multielement arrays.Architectural modifications reducing the interaction effect different radiating apertures.

Dynamics of laser produced silver plasma under film deposition conditions studied using optical emission spectroscopy

Laser produced plasma from silver is generated using a Q-switched Nd:YAG laser. Optical emission spectroscopy is used to carry out time of flight (TOF) analysis of atomic particles. An anomalous double peak profile in the TOF distribution is observed at low pressure. A collection of slower species emerge at reduced pressure below 4 X lO-3 mbar and this species has a greater velocity spread. At high pressure the plasma expansion follows the shockwave model with cylindrical symmetry whereas at reduced pressure it shows unsteady adiabatic expansion (UAE). During UAE the species show a parabolic increases in the expansion time with radial distance whereas during shock wave expansion the exponent is less than one. The angular distribution of the ablated species in the plume is obtained from the measurement of optical density of thin films deposited on to glass substrates kept perpendicular to the plume. There is a sharp variation in the film thickness away from the film centre due to asymmetries in the plume.

Prompt electron emission and collisional ionization of ambient gas during pulsed laser ablation of silver

A silver target kept under partial vacuum conditions was irradiated with focused nanosecond pulses at 1:06 mm from a Nd:YAG laser. The electron emission monitored with a Langmuir probe shows a clear twin-peak distribution. The first peak which is very sharp has only a small delay and it indicates prompt electron emission with energy as much as 60 5 eV. Also the prompt electron emission shows a temporal profile with a width that is same as that for the laser pulse whereas the second peak is broader, covers several microseconds, and represents the low-energy electrons (2 0:5 eV) associated with the laser-induced silver plasma as revealed by time-of-flight measurements. It has been found that prompt electrons ejected from the target collisionally excite and ionize ambient gas molecules. Clearly resolved rotational structure is observed in the emission spectra of ambient nitrogen molecules. Combined with time-resolved spectroscopy, the prompt electrons can be used as excitation sources for various collisional excitation–relaxation experiments. The electron density corresponding to the first peak is estimated to be of the order of 1017 cm?--3 and it is found that the density increases as a function of distance away from the target. Dependence of probe current on laser intensity shows plasma shielding at high laser intensities.