Crystal Structures and Spectral Investigation of Aroylhydrazones and their Mixed Ligand Metal Chelates

Supra molecular architectures of coordination complexes of liydrazones through non covalent interactions have been explored. Molecular self—assernbly driven by weak interactions such as hydrogen— bonding, K '”T[, C-1-I‘ "TE, van der Waals interactions, and so forth are currently of tremendous research interest in the fields of molecule based materials. The directional properties of the hydrogembonding interaction associate discrete molecules into aggregate structures that are sufficiently stable to be considered as independent chemical species. Chemistry can borrow nature’s strategy to utilize hydrogen-bonding as Well as other noncovalent interactions as found in secondary and tertiary structures of proteins such as the double helix folding of DNA, hydrophobic selflorganization of phospholipids in cell membrane etc. In supramolecular chemistry hydrogen bonding plays an important role in forming a variety of architectures. Thus, the wise modulation and tuning of the complementary sites responsible for hydrogen—bond formation have led to its application in supramolecular electronics, host-guest chemistry, self-assembly of molecular capsules, nanotubes etc. The work presented in this thesis describes the synthesis and characterization of metal complexes derived from some substituted aroylhydrazones. The thesis is divided into seven chapters.

Mono- and binuclear transition metal complexes of n(4)-substituted thiosel\licarbazones derived frol\i salicylaldehyde and 2-hydroxyacetophenone synthesis, spectral and structural studies

The work embodied in the thesis is divided into eight chapters. Chapter I gives a brief introduction about metal complexes of thiosemicarbazones, including their structural and bonding properties. Chapter 2 deals with the synthesis and single crystal X-ray diffraction studies of various thiosemicarbazones used up for the present investigations and various characterization techniques. Chapter 3 deals with synthesis, spectral and structural studies of Cu(U) complexes with ONS donor thiosemicarbazones. Chapter 4 deals with synthesis and spectral studies of Ni(II) complexes \vith 2-hydroxyacetophenone N(4)-cyclohexyl thiosemicarbazone as the ligand. Chapter 5 includes synthesis and spectral studies of Mn(II) complexes. Chapter 6 deals with synthesis, spectral and structural studies of Zn(II) complexes. Chapter 7 includes synthesis and spectral studies of oxovanadium(IV) complexes. Chapter 8 deals with synthesis, spectral and single crystal X-ray diffraction studies of dioxomolybdenum(VI) complexes.

Synthesis, characterization and physiochemical information, along with antimicrobial studies of some metal complexes derived from an ON donor semicarbazone ligand

Eight new transition metal complexes of benzaldehyde-N(4)–phenylsemicarbazone have been synthesized and characterized by elemental analyses, molar conductance, electronic and infrared spectral studies. In all the complexes, the semicarbazone is coordinated as neutral bidentate ligand. 1H NMR spectrum of [Zn(HL)2(OAc)2] shows that there is no enolisation of the ligand in the complex. The magnetic susceptibility measurements indicate that Cr(III), Mn(II), Fe(III), Co(II) and Cu(II) complexes are paramagnetic and Ni(II) is diamagnetic. The EPR spectrum of [Mn(HL)2(OAc)2] in DMF solution at 77K shows hyperfine sextet with low intensity forbidden lines lying between each of the two main hyperfine lines. The g values calculated for the [Cu(HL)2SO4] complex in frozen DMF, indicate the presence of unpaired electron in the dx2−y2 orbital. The metal ligand bonding parameters evaluated showed strong in-plane bonding and in-plane bonding. The ligand and complexes were screened for their possible antimicrobial activities.

Low-Cost Micromechanically Tunable Optical Devices: Strained Resonator Engineering, Technological Implementation and Characterization

The rapid growth of the optical communication branches and the enormous demand for more bandwidth require novel networks such as dense wavelength division multiplexing (DWDM). These networks enable higher bitrate transmission using the existing optical fibers. Micromechanically tunable optical microcavity devices like VCSELs, Fabry-Pérot filters and photodetectors are core components of these novel DWDM systems. Several air-gap based tunable devices were successfully implemented in the last years. Even though these concepts are very promising, two main disadvantages are still remaining. On the one hand, the high fabrication and integration cost and on the other hand the undesired adverse buckling of the suspended membranes. This thesis addresses these two problems and consists of two main parts: • PECVD dielectric material investigation and stress control resulting in membranes shape engineering. • Implementation and characterization of novel tunable optical devices with tailored shapes of the suspended membranes. For this purposes, low-cost PECVD technology is investigated and developed in detail. The macro- and microstress of silicon nitride and silicon dioxide are controlled over a wide range. Furthermore, the effect of stress on the optical and mechanical properties of the suspended membranes and on the microcavities is evaluated. Various membrane shapes (concave, convex and planar) with several radii of curvature are fabricated. Using this resonator shape engineering, microcavity devices such as non tunable and tunable Fabry-Pérot filters, VCSELs and PIN photodetectors are succesfully implemented. The fabricated Fabry-Pérot filters cover a spectral range of over 200nm and show resonance linewidths down to 1.5nm. By varying the stress distribution across the vertical direction within a DBR, the shape and the radius of curvature of the top membrane are explicitely tailored. By adjusting the incoming light beam waist to the curvature, the fundamental resonant mode is supported and the higher order ones are suppressed. For instance, a tunable VCSEL with 26 nm tuning range, 400µW maximal output power, 47nm free spectral range and over 57dB side mode suppresion ratio (SMSR) is demonstrated. Other technologies, such as introducing light emitting organic materials in microcavities are also investigated.

Large-Size AlGaN/GaN HEMT Large-Signal Electrothermal Characterization and Modeling for Wireless Digital Communications

The rapid growth in high data rate communication systems has introduced new high spectral efficient modulation techniques and standards such as LTE-A (long term evolution-advanced) for 4G (4th generation) systems. These techniques have provided a broader bandwidth but introduced high peak-to-average power ratio (PAR) problem at the high power amplifier (HPA) level of the communication system base transceiver station (BTS). To avoid spectral spreading due to high PAR, stringent requirement on linearity is needed which brings the HPA to operate at large back-off power at the expense of power efficiency. Consequently, high power devices are fundamental in HPAs for high linearity and efficiency. Recent development in wide bandgap power devices, in particular AlGaN/GaN HEMT, has offered higher power level with superior linearity-efficiency trade-off in microwaves communication. For cost-effective HPA design to production cycle, rigorous computer aided design (CAD) AlGaN/GaN HEMT models are essential to reflect real response with increasing power level and channel temperature. Therefore, large-size AlGaN/GaN HEMT large-signal electrothermal modeling procedure is proposed. The HEMT structure analysis, characterization, data processing, model extraction and model implementation phases have been covered in this thesis including trapping and self-heating dispersion accounting for nonlinear drain current collapse. The small-signal model is extracted using the 22-element modeling procedure developed in our department. The intrinsic large-signal model is deeply investigated in conjunction with linearity prediction. The accuracy of the nonlinear drain current has been enhanced through several issues such as trapping and self-heating characterization. Also, the HEMT structure thermal profile has been investigated and corresponding thermal resistance has been extracted through thermal simulation and chuck-controlled temperature pulsed I(V) and static DC measurements. Higher-order equivalent thermal model is extracted and implemented in the HEMT large-signal model to accurately estimate instantaneous channel temperature. Moreover, trapping and self-heating transients has been characterized through transient measurements. The obtained time constants are represented by equivalent sub-circuits and integrated in the nonlinear drain current implementation to account for complex communication signals dynamic prediction. The obtained verification of this table-based large-size large-signal electrothermal model implementation has illustrated high accuracy in terms of output power, gain, efficiency and nonlinearity prediction with respect to standard large-signal test signals.

Characterization of Novel Fabry Pérot Filter Arrays for Nanospectrometers in Medical Applications

Optische Spektroskopie ist eine sehr wichtige Messtechnik mit einem hohen Potential für zahlreiche Anwendungen in der Industrie und Wissenschaft. Kostengünstige und miniaturisierte Spektrometer z.B. werden besonders für moderne Sensorsysteme “smart personal environments” benötigt, die vor allem in der Energietechnik, Messtechnik, Sicherheitstechnik (safety and security), IT und Medizintechnik verwendet werden. Unter allen miniaturisierten Spektrometern ist eines der attraktivsten Miniaturisierungsverfahren das Fabry Pérot Filter. Bei diesem Verfahren kann die Kombination von einem Fabry Pérot (FP) Filterarray und einem Detektorarray als Mikrospektrometer funktionieren. Jeder Detektor entspricht einem einzelnen Filter, um ein sehr schmales Band von Wellenlängen, die durch das Filter durchgelassen werden, zu detektieren. Ein Array von FP-Filter wird eingesetzt, bei dem jeder Filter eine unterschiedliche spektrale Filterlinie auswählt. Die spektrale Position jedes Bandes der Wellenlänge wird durch die einzelnen Kavitätshöhe des Filters definiert. Die Arrays wurden mit Filtergrößen, die nur durch die Array-Dimension der einzelnen Detektoren begrenzt werden, entwickelt. Allerdings erfordern die bestehenden Fabry Pérot Filter-Mikrospektrometer komplizierte Fertigungsschritte für die Strukturierung der 3D-Filter-Kavitäten mit unterschiedlichen Höhen, die nicht kosteneffizient für eine industrielle Fertigung sind. Um die Kosten bei Aufrechterhaltung der herausragenden Vorteile der FP-Filter-Struktur zu reduzieren, wird eine neue Methode zur Herstellung der miniaturisierten FP-Filtern mittels NanoImprint Technologie entwickelt und präsentiert. In diesem Fall werden die mehreren Kavitäten-Herstellungsschritte durch einen einzigen Schritt ersetzt, die hohe vertikale Auflösung der 3D NanoImprint Technologie verwendet. Seit dem die NanoImprint Technologie verwendet wird, wird das auf FP Filters basierende miniaturisierte Spectrometer nanospectrometer genannt. Ein statischer Nano-Spektrometer besteht aus einem statischen FP-Filterarray auf einem Detektorarray (siehe Abb. 1). Jeder FP-Filter im Array besteht aus dem unteren Distributed Bragg Reflector (DBR), einer Resonanz-Kavität und einen oberen DBR. Der obere und untere DBR sind identisch und bestehen aus periodisch abwechselnden dünnen dielektrischen Schichten von Materialien mit hohem und niedrigem Brechungsindex. Die optischen Schichten jeder dielektrischen Dünnfilmschicht, die in dem DBR enthalten sind, entsprechen einen Viertel der Design-Wellenlänge. Jeder FP-Filter wird einer definierten Fläche des Detektorarrays zugeordnet. Dieser Bereich kann aus einzelnen Detektorelementen oder deren Gruppen enthalten. Daher werden die Seitenkanal-Geometrien der Kavität aufgebaut, die dem Detektor entsprechen. Die seitlichen und vertikalen Dimensionen der Kavität werden genau durch 3D NanoImprint Technologie aufgebaut. Die Kavitäten haben Unterschiede von wenigem Nanometer in der vertikalen Richtung. Die Präzision der Kavität in der vertikalen Richtung ist ein wichtiger Faktor, der die Genauigkeit der spektralen Position und Durchlässigkeit des Filters Transmissionslinie beeinflusst.

Syntheses, characterization and X-ray crystal structures of Ni(II) complexes of tridentate monocondensed and tetradentate dicondensed Schiff bases

Two octahedral complexes [Ni(HL1)(2)](ClO4)(2) (1) and [Ni(HL2)(2)](ClO4)(2) (2) and a square planar complex [Ni(HL3)]ClO4 (3) have been prepared, where [HL1 = 3-(2-amino-ethylimino)-butan-2-one oxime, HL2 = 3-(2-amino-propylimino)butan-2-one oxime] and H2L3 = 3-[2-(3-hydroxy-1-methyl-but-2-enylideneamino)-1-methyl-ethylimino]-buta n-2-one oxime. All the complexes have been characterized by elemental analyses, spectral studies and room temperature magnetic moment measurements. The molecular structures of all three compounds were elucidated on the basis of X-ray crystallography: complexes 1 and 2 are seen to be the met isomers. (C) 2008 Elsevier Ltd. All rights reserved.

Spectral characterisation of cooled filters for remote sensing

The improvements obtained on cooling atmospheric remote-sensing instruments for space flight applications has promoted research in characterization of the necessary optical filters. By modelling the effects of temperature on the dispersive spectrum of some constituent thin film materials, the cooled performance can be simulated and compared. multilayer filter designs with the measured spectra from actual filters. Two actual filters are discussed, for the 7µm region, one a composite cut-on/cut-off design of 13% HBW and the other an integral narrowband design of 4% HBW.

Coordination behavior of symmetrical hexadentate O2N2S2-donor Schiff bases toward zinc (II): synthesis, characterization, and crystal structure

Two series of zinc(II) complexes of two Schiff bases (H2L1 and H2L2) formulated as [Zn(HL1/HL2)]ClO4 (1a and 1b) and [Zn(L1/L2)] (2a and 2b), where H2L1 = 1,8-bis(salicylideneamino)-3,6-dithiaoctane and H2L2 = 1,9-bis(salicylideneamino)-3,7-dithianonane, have been prepared and isolated in pure form by changing the chemical environment. Elemental, spectral, and other physicochemical results characterize the complexes. A single crystal X-ray diffraction study confirms the structure of [Zn(HL1)]ClO4 (1a). In 1a, zinc(II) has a distorted octahedral environment with a ZnO2N2S2 chromophore.

Synthesis and characterization of Cu(II) complexes of tetradentate and tridentate symmetrical Schiff base ligands involving o-phenelenediamine, salicylaldehyde and diacetylmonoxime

A mononuclear complex [CuL] (1), a binuclear complex [Cu2LCl2(H2O)] (2), a trinuclear complex [Cu3L2](ClO4)(2) (3) involving o-phenylenediamine and salicylaldehyde and another binuclear complex of a tridentate ligand (H2L1) [Cu2L (2) (1) ](CH3COO)(2) (4) involving o-phenylenediamine and diacetylmonoxime have been synthesized, where H2L = N,N'-o-phenylenebis(salicylideneimine) and H2L1 = 3-(2-aminophenylimino)butan-2-one oxime. All the complexes have been characterized by elemental analyses, spectral and magnetic studies. The binuclear complex (2) was characterized structurally where the two Cu(II) centers are connected via an oxygen-bridged arrangement.

Characterization of a highly biodiverse floodplain meadow using hyperspectral remote sensing within a plant functional trait framework

We assessed the potential for using optical functional types as effective markers to monitor changes in vegetation in floodplain meadows associated with changes in their local environment. Floodplain meadows are challenging ecosystems for monitoring and conservation because of their highly biodiverse nature. Our aim was to understand and explain spectral differences among key members of floodplain meadows and also characterize differences with respect to functional traits. The study was conducted on a typical floodplain meadow in UK (MG4-type, mesotrophic grassland type 4, according to British National Vegetation Classification). We compared two approaches to characterize floodplain communities using field spectroscopy. The first approach was sub-community based, in which we collected spectral signatures for species groupings indicating two distinct eco-hydrological conditions (dry and wet soil indicator species). The other approach was “species-specific”, in which we focused on the spectral reflectance of three key species found on the meadow. One herb species is a typical member of the MG4 floodplain meadow community, while the other two species, sedge and rush, represent wetland vegetation. We also monitored vegetation biophysical and functional properties as well as soil nutrients and ground water levels. We found that the vegetation classes representing meadow sub-communities could not be spectrally distinguished from each other, whereas the individual herb species was found to have a distinctly different spectral signature from the sedge and rush species. The spectral differences between these three species could be explained by their observed differences in plant biophysical parameters, as corroborated through radiative transfer model simulations. These parameters, such as leaf area index, leaf dry matter content, leaf water content, and specific leaf area, along with other functional parameters, such as maximum carboxylation capacity and leaf nitrogen content, also helped explain the species’ differences in functional dynamics. Groundwater level and soil nitrogen availability, which are important factors governing plant nutrient status, were also found to be significantly different for the herb/wetland species’ locations. The study concludes that spectrally distinguishable species, typical for a highly biodiverse site such as a floodplain meadow, could potentially be used as target species to monitor vegetation dynamics under changing environmental conditions.

Synthesis, characterization, crystal structure, and DNA-binding of ruthenium(II) complexes of heterocyclic nitrogen ligands resulting from a benzimidazole-based quinazoline derivative

The reaction of cis-[RuCl2(dmso)(4)] with [6-(2-pyridinyl)-5,6-dihydrobenzimidazo[1,2-c] quinazoline] (L) afforded in pure form a blue ruthenium(II) complex, [Ru(L-1)(2)] (1), where the original L changed to [2-(1H-benzoimidazol-2-yl)-phenyl]-pyridin-2-ylmethylene-amine (HL1). Treatment of RuCl3 center dot 3H(2)O with L in dry tetrahydrofuran in inert atmosphere led to a green ruthenium(II) complex, trans-[RuCl2(L-2)(2)] (2), where L was oxidized in situ to the neutral species 6-pyridin-yl-benzo[4,5]imidazo[1,2-c] quinazoline (L-2). Complex 2 was also obtained from the reaction of RuCl3 center dot 3H(2)O with L-2 in dry ethanol. Complexes 1 and 2 have been characterized by physico-chemical and spectroscopic tools, and 1 has been structurally characterized by single-crystal X-ray crystallography. The electrochemical behavior of the complexes shows the Ru(III)/Ru(II) couple at different potentials with quasi-reversible voltammograms. The interaction of these complexes with calf thymus DNA by using absorption and emission spectral studies allowed determination of the binding constant K-b and the linear Stern-Volmer quenching constant K-SV

Characterization and antimicrobial efficacy against E. coli of a helium/air plasma at atmospheric pressure created in a plastic package

A plasma source, sustained by the application of a floating high voltage (±15 kV) to parallel-plate electrodes at 50 Hz, has been achieved in a helium/air mixture at atmospheric pressure (P = 105 Pa) contained in a zip-locked plastic package placed in the electrode gap. Some of the physical and antimicrobial properties of this apparatus were established with a view to ascertain its performance as a prototype for the disinfection of fresh produce. The current–voltage (I–V) and charge–voltage (Q–V) characteristics of the system were measured as a function of gap distance d, in the range (3 × 103 ≤ Pd ≤ 1.0 × 104 Pa m). The electrical measurements showed this plasma source to exhibit the characteristic behaviour of a dielectric barrier discharge in the filamentary mode and its properties could be accurately interpreted by the two-capacitance in series model. The power consumed by the discharge and the reduced field strength were found to decrease quadratically from 12.0 W to 4.5 W and linearly from 140 Td to 50 Td, respectively, in the range studied. Emission spectra of the discharge were recorded on a relative intensity scale and the dominant spectral features could be assigned to strong vibrational bands in the 2+ and 1− systems of N2 and ${\rm N}_2^+$ , respectively, with other weak signatures from the NO and OH radicals and the N+, He and O atomic species. Absolute spectral intensities were also recorded and interpreted by comparison with the non-equilibrium synthetic spectra generated by the computer code SPECAIR. At an inter-electrode gap of 0.04 m, this comparison yielded typical values for the electron, vibrational and translational (gas) temperatures of (4980 ± 100) K, (2700 ± 200) K and (300 ± 100) K, respectively and an electron density of 1.0 × 1017 m−3. A Boltzmann plot also provided a value of (3200 ± 200 K) for the vibrational temperature. The antimicrobial efficacy was assessed by studying the resistance of both Escherichia coli K12 its isogenic mutants in soxR, soxS, oxyR, rpoS and dnaK selected to identify possible cellular responses and targets related with 5 min exposure to the active gas in proximity of, but not directly in, the path of the discharge filaments. Both the parent strain and mutants populations were significantly reduced by more than 1.5 log cycles in these conditions, showing the potential of the system. Post-treatment storage studies showed that some transcription regulators and specific genes related to oxidative stress play an important role in the E. coli repair mechanism and that plasma exposure affects specific cell regulator systems.

Characterization of the optical properties of atmospheric aerosols in Amazonia from long-term AERONET monitoring (1993-1995 and 1999-2006)

We present a new climatology of atmospheric aerosols (primarily pyrogenic and biogenic) for the Brazilian tropics on the basis of a high-quality data set of spectral aerosol optical depth and directional sky radiance measurements from Aerosol Robotic Network (AERONET) Cimel Sun-sky radiometers at more than 15 sites distributed across the Amazon basin and adjacent Cerrado region. This network is the only long-term project (with a record including observations from more than 11 years at some locations) ever to have provided ground-based remotely-sensed column aerosol properties for this critical region. Distinctive features of the Amazonian area aerosol are presented by partitioning the region into three aerosol regimes: southern Amazonian forest, Cerrado, and northern Amazonian forest. The monitoring sites generally include measurements from the interval 1999-2006, but some sites have measurement records that date back to the initial days of the AERONET program in 1993. Seasonal time series of aerosol optical depth (AOD), angstrom ngstrom exponent, and columnar-averaged microphysical properties of the aerosol derived from sky radiance inversion techniques (single-scattering albedo, volume size distribution, fine mode fraction of AOD, etc.) are described and contrasted for the defined regions. During the wet season, occurrences of mineral dust penetrating deep into the interior were observed.

Characterization and spectroscopic analysis of phenol-ethanol hydrogen bonded clusters

Different hydrogen bonded clusters involving phenol and ethanol are studied theoretically using MP2/aug-cc-pVDZ. Nine different 1: 1 clusters are obtained and analyzed according to their stability and spectroscopic properties. Different isomeric forms of ethanol are considered. Attention is also devoted to the spectral shift of the characteristic pi -> pi* transition of phenol. Using TDHF, CIS, CIS(D) and TDB3LYP in aug-cc-pVDZ basis set, all results agree that a red shift is obtained when phenol is the hydrogen donor and a blue shift is obtained in the opposite case. These results are used to rationalize the red shift observed for phenol in liquid ethanol. (C) 2010 Elsevier B.V. All rights reserved.