Nonlinear distortion generation mechanisms in Doherty amplifiers

Nowadays, wireless communications systems demand for greater mobility and higher data rates. Moreover, the need for spectral efficiency requires the use of non-constant envelope modulation schemes. Hence, power amplifier designers have to build highly efficient, broadband and linear amplifiers. In order to fulfil these strict requirements, the practical Doherty amplifier seems to be the most promising technique. However, due to its complex operation, its nonlinear distortion generation mechanisms are not yet fully understood. Currently, only heuristic interpretations are being used to justify the observed phenomena. Therefore, the main objective of this work is to provide a model capable of describing the Doherty power amplifier nonlinear distortion generation mechanisms, allowing the optimization of its design according to linearity and efficiency criteria. Besides that, this approach will allow a bridge between two different worlds: power amplifier design and digital pre-distortion since the knowledge gathered from the Doherty operation will serve to select the most suitable pre-distortion models.

Class-D audio amplifiers with negative feedback

There are many different designs for audio amplifiers. Class-D, or switching, amplifiers generate their output signal in the form of a high-frequency square wave of variable duty cycle (ratio of on time to off time). The square-wave nature of the output allows a particularly efficient output stage, with minimal losses. The output is ultimately filtered to remove components of the spectrum above the audio range. Mathematical models are derived here for a variety of related class-D amplifier designs that use negative feedback. These models use an asymptotic expansion in powers of a small parameter related to the ratio of typical audio frequencies to the switching frequency to develop a power series for the output component in the audio spectrum. These models confirm that there is a form of distortion intrinsic to such amplifier designs. The models also explain why two approaches used commercially succeed in largely eliminating this distortion; a new means of overcoming the intrinsic distortion is revealed by the analysis. Copyright (2006) Society for Industrial and Applied Mathematics

High-Throughput Prediction of Acacia and Eucalypt Lignin Syringyl/Guaiacyl Content Using FT-Raman Spectroscopy and Partial Least Squares Modeling

High-throughput techniques are necessary to efficiently screen potential lignocellulosic feedstocks for the production of renewable fuels, chemicals, and bio-based materials, thereby reducing experimental time and expense while supplanting tedious, destructive methods. The ratio of lignin syringyl (S) to guaiacyl (G) monomers has been routinely quantified as a way to probe biomass recalcitrance. Mid-infrared and Raman spectroscopy have been demonstrated to produce robust partial least squares models for the prediction of lignin S/G ratios in a diverse group of Acacia and eucalypt trees. The most accurate Raman model has now been used to predict the S/G ratio from 269 unknown Acacia and eucalypt feedstocks. This study demonstrates the application of a partial least squares model composed of Raman spectral data and lignin S/G ratios measured using pyrolysis/molecular beam mass spectrometry (pyMBMS) for the prediction of S/G ratios in an unknown data set. The predicted S/G ratios calculated by the model were averaged according to plant species, and the means were not found to differ from the pyMBMS ratios when evaluating the mean values of each method within the 95 % confidence interval. Pairwise comparisons within each data set were employed to assess statistical differences between each biomass species. While some pairwise appraisals failed to differentiate between species, Acacias, in both data sets, clearly display significant differences in their S/G composition which distinguish them from eucalypts. This research shows the power of using Raman spectroscopy to supplant tedious, destructive methods for the evaluation of the lignin S/G ratio of diverse plant biomass materials. © 2015, The Author(s).

Raman Spectroscopy and DFT calculations for the Electronic Structure Characterization of Conjugated Polymers

In the last three decades, there has been a broad academic and industrial interest in conjugated polymers as semiconducting materials for organic electronics. Their applications in polymer light-emitting diodes (PLEDs), polymer solar cells (PSCs), and organic field-effect transistors (OFETs) offer opportunities for the resolution of energy issues as well as the development of display and information technologies1. Conjugated polymers provide several advantages including low cost, light weight, good flexibility, as well as solubility which make them readily processed and easily printed, removing the conventional photolithography for patterning2. A large library of polymer semiconductors have been synthesized and investigated with different building blocks, such as acenes or thiophene and derivatives, which have been employed to design new materials according to individual demands for specific applications. To design ideal conjugated polymers for specific applications, some general principles should be taken into account, including (i) side chains (ii) molecular weights, (iii) band gap and HOMO and LUMO energy levels, and (iv) suited morphology.3-6 The aim of this study is to elucidate the impact that substitution exerts on the molecular and electronic structure of π-conjugated polymers with outstanding performances in organic electronic devices. Different configurations of the π-conjugated backbones are analyzed: (i) donor-acceptor configuration, (ii) 1D lineal or 2D branched conjugated backbones, and (iii) encapsulated polymers (see Figure 1). Our combined vibrational spectroscopy and DFT study shows that small changes in the substitution pattern and in the molecular configuration have a strong impact on the electronic characteristics of these polymers. We hope this study can advance useful structure-property relationships of conjugated polymers and guide the design of new materials for organic electronic applications.

Raman spectroscopy study of the transformation of the carbonaceous skeleton of a polymer-based nanoporous carbon along the thermal annealing pathway

We report a multi-wavelength Raman spectroscopy study of the structural changes along the thermal annealing pathway of a poly(furfuryl alcohol) (PFA) derived nanoporous carbon (NPC). The Raman spectra were deconvoluted utilizing G, D, D′, A and TPA bands. The appropriateness of these deconvolutions was confirmed via recovery of the correct dispersive behaviours of these bands. It is proposed that the ID/IG ratio is composed of two parts: one associated with the extent of graphitic crystallites (the Tuinstra–Koenig relationship), and a second related to the inter-defect distance. This model was used to successfully determine the variation of the in-plane size and intra-plane defect density along the annealing pathway. It is proposed that the NPC skeleton evolves along the annealing pathway in two stages: below 1600 °C it was dominated by a reduction of in-plane defects with a minor crystallite growth, and above this temperature growth of the crystallites accelerates as the in-plane defect density approaches zero. A significant amount of transpolyacetylene (TPA)-like structures was found to be remaining even at 2400 °C. These may be responsible for resistance to further graphitization of the PFA-based carbon at higher temperatures.

Characterization of a zeolite-templated carbon by electrochemical quartz crystal microbalance and in situ Raman spectroscopy

Electrochemical quartz crystal microbalance was used to monitor the mass changes during the electrochemical characterization of a zeolite-templated carbon (ZTC) in 1 M H2SO4 medium. Under electrochemical oxidation conditions, a high anodic current and a net mass increase were recorded, resulting in the increase of the specific capacitance owing to the contribution of the pseudocapacitance, mainly derived from the hydroquinone–quinone redox couple. Under more severe electrochemical conditions, a net mass loss was observed, revealing that electrochemical gasification took place. Surface chemistry, before and after the electrochemical treatments, was analyzed through temperature programmed desorption experiments. Furthermore, in situ Raman spectroscopy was used to further characterize the structural changes produced in ZTC under the electrochemical conditions applied, supporting that high potential values produce the electrochemical oxidation and degradation of the carbon material.

Amplification d’impulsions brèves de haute énergie par effet Raman stimulé dans les fibres optiques

Le développement au cours des dernières décennies de lasers à fibre à verrouillage de modes permet aujourd’hui d’avoir accès à des sources fiables d’impulsions femtosecondes qui sont utilisées autant dans les laboratoires de recherche que pour des applications commerciales. Grâce à leur large bande passante ainsi qu’à leur excellente dissipation de chaleur, les fibres dopées avec des ions de terres rares ont permis l’amplification et la génération d’impulsions brèves de haute énergie avec une forte cadence. Cependant, les effets non linéaires causés par la faible taille du faisceau dans la fibre ainsi que la saturation de l’inversion de population du milieu compliquent l’utilisation d’amplificateurs fibrés pour l’obtention d’impulsions brèves dont l’énergie dépasse le millijoule. Diverses stratégies comme l’étirement des impulsions à des durées de l’ordre de la nanoseconde, l’utilisation de fibres à cristaux photoniques ayant un coeur plus large et l’amplification en parallèle ont permis de contourner ces limitations pour obtenir des impulsions de quelques millijoules ayant une durée inférieure à la picoseconde. Ce mémoire de maîtrise présente une nouvelle approche pour l’amplification d’impulsions brèves utilisant la diffusion Raman des verres de silice comme milieu de gain. Il est connu que cet effet non linéaire permet l’amplification avec une large bande passante et ce dernier est d’ailleurs couramment utilisé aujourd’hui dans les réseaux de télécommunications par fibre optique. Puisque l’adaptation des schémas d’amplification Raman existants aux impulsions brèves de haute énergie n’est pas directe, on propose plutôt un schéma consistant à transférer l’énergie d’une impulsion pompe quasi monochromatique à une impulsion signal brève étirée avec une dérive en fréquence. Afin d’évaluer le potentiel du gain Raman pour l’amplification d’impulsions brèves, ce mémoire présente un modèle analytique permettant de prédire les caractéristiques de l’impulsion amplifiée selon celles de la pompe et le milieu dans lequel elles se propagent. On trouve alors que la bande passante élevée du gain Raman des verres de silice ainsi que sa saturation inhomogène permettent l’amplification d’impulsions signal à une énergie comparable à celle de la pompe tout en conservant une largeur spectrale élevée supportant la compression à des durées très brèves. Quelques variantes du schéma d’amplification sont proposées, et leur potentiel est évalué par l’utilisation du modèle analytique ou de simulations numériques. On prédit analytiquement et numériquement l’amplification Raman d’impulsions à des énergies de quelques millijoules, dont la durée est inférieure à 150 fs et dont la puissance crête avoisine 20 GW.

Evaluation of portable Raman spectroscopy and handheld X-ray fluorescence analysis (hXRF) for the direct analysis of glyptics

In archaeometry, the advantages of a combined use of Raman spectroscopy and X-ray fluorescence spectroscopy are extensively discussed for applications such as the analysis of paintings, manuscripts, pottery, etc. Here, we demonstrate for the first time the advantage of using both techniques for analysing glyptics. These engraved gemstones or glass materials were originally used as stamps, to identify the owner, for instance on letters, but also on wine vessels. For this research, a set of 64 glyptics (42 Roman glass specimens and 22 modern ones), belonging to the collection of the museum ‘Quinta das Cruzes’ in Funchal (Madeira, Portugal), was analysed with portable Raman spectroscopy and handheld X-ray fluorescence (hXRF). These techniques were also used to confirm the gemological identification of these precious objects and can give extra information about the glass composition. Raman spectroscopy identifies the molecular composition as well as on the crystalline phases present. On the other hand, hXRF results show that the antique Roman glass samples are characterised with low Pb and Sn levels and that the modern specimens can be discriminated in two groups: lead-based and non-lead-based ones.

Graphene And Carbon Nanotube Nanocomposite For Gene Transfection.

Graphene and carbon nanotube nanocomposite (GCN) was synthesised and applied in gene transfection of pIRES plasmid conjugated with green fluorescent protein (GFP) in NIH-3T3 and NG97 cell lines. The tips of the multi-walled carbon nanotubes (MWCNTs) were exfoliated by oxygen plasma etching, which is also known to attach oxygen content groups on the MWCNT surfaces, changing their hydrophobicity. The nanocomposite was characterised by high resolution scanning electron microscopy; energy-dispersive X-ray, Fourier transform infrared and Raman spectroscopies, as well as zeta potential and particle size analyses using dynamic light scattering. BET adsorption isotherms showed the GCN to have an effective surface area of 38.5m(2)/g. The GCN and pIRES plasmid conjugated with the GFP gene, forming π-stacking when dispersed in water by magnetic stirring, resulting in a helical wrap. The measured zeta potential confirmed that the plasmid was connected to the nanocomposite. The NIH-3T3 and NG97 cell lines could phagocytize this wrap. The gene transfection was characterised by fluorescent protein produced in the cells and pictured by fluorescent microscopy. Before application, we studied GCN cell viability in NIH-3T3 and NG97 line cells using both MTT and Neutral Red uptake assays. Our results suggest that GCN has moderate stability behaviour as colloid solution and has great potential as a gene carrier agent in non-viral based therapy, with low cytotoxicity and good transfection efficiency.

Carbon Nanoparticles For Gene Transfection In Eukaryotic Cell Lines.

For the first time, oxygen terminated cellulose carbon nanoparticles (CCN) was synthesised and applied in gene transfection of pIRES plasmid. The CCN was prepared from catalytic of polyaniline by chemical vapour deposition techniques. This plasmid contains one gene that encodes the green fluorescent protein (GFP) in eukaryotic cells, making them fluorescent. This new nanomaterial and pIRES plasmid formed π-stacking when dispersed in water by magnetic stirring. The frequencies shift in zeta potential confirmed the plasmid strongly connects to the nanomaterial. In vitro tests found that this conjugation was phagocytised by NG97, NIH-3T3 and A549 cell lines making them fluorescent, which was visualised by fluorescent microscopy. Before the transfection test, we studied CCN in cell viability. Both MTT and Neutral Red uptake tests were carried out using NG97, NIH-3T3 and A549 cell lines. Further, we use metabolomics to verify if small amounts of nanomaterial would be enough to cause some cellular damage in NG97 cells. We showed two mechanisms of action by CCN-DNA complex, producing an exogenous protein by the transfected cell and metabolomic changes that contributed by better understanding of glioblastoma, being the major finding of this work. Our results suggested that this nanomaterial has great potential as a gene carrier agent in non-viral based therapy, with low cytotoxicity, good transfection efficiency, and low cell damage in small amounts of nanomaterials in metabolomic tests.

On The Distinct Molecular Architectures Of Dipping- And Spray-lbl Films Containing Lipid Vesicles.

The introduction of spraying procedures to fabricate layer-by-layer (LbL) films has brought new possibilities for the control of molecular architectures and for making the LbL technique compliant with industrial processes. In this study we show that significantly distinct architectures are produced for dipping and spray-LbL films of the same components, which included DODAB/DPPG vesicles. The films differed notably in their thickness and stratified nature. The electrical response of the two types of films to aqueous solutions containing erythrosin was also different. With multidimensional projections we showed that the impedance for the DODAB/DPPG spray-LbL film is more sensitive to changes in concentration, being therefore more promising as sensing units. Furthermore, with surface-enhanced Raman scattering (SERS) we could ascribe the high sensitivity of the LbL films to adsorption of erythrosin.