Rapid Scan Electron Paramagnetic Resonance (EPR) and Digital EPR Development

Rapid scan electron paramagnetic resonance (EPR) was developed in the Eaton laboratory at the University of Denver. Applications of rapid scan to wider spectra, such as for immobilized nitroxides, spin-labeled proteins, irradiated tooth and fingernail samples were demonstrated in this dissertation. The scan width has been increased from 55 G to 160 G. The signal to noise (S/N) improvement for slowly tumbling spin-labeled protein samples that is provided by rapid scan EPR will be highly advantageous for biophysical studies. With substantial improvement in S/N by rapid scan, the dose estimation for irradiated tooth enamels became more reliable than the traditional continuous wave (CW) EPR. An alternate approach of rapid scan, called field-stepped direct detection EPR, was developed to reconstruct wider EPR signals. A Mn2+ containing crystal was measured by field-stepped direct detection EPR, which had a spectrum more than 6000 G wide. Since the field-stepped direct detection extends the advantages of rapid scan to much wider scan ranges, this methodology has a great potential to replace the traditional CW EPR. With recent advances in digital electronics, a digital rapid scan spectrometer was built based on an arbitrary waveform generator (AWG), which can excite spins and detect EPR signals with a fully digital system. A near-baseband detection method was used to acquire the in-phase and quadrature signals in one physical channel. The signal was analyzed digitally to generate ideally orthogonal quadrature signals. A multiharmonic algorithm was developed that employed harmonics of the modulation frequencies acquired in the spectrometer transient mode. It was applied for signals with complicated lineshapes, and can simplify the selection of modulation amplitude. A digital saturation recovery system based on an AWG was built at X-band (9.6 GHz). To demonstrate performance of the system, the spin-lattice relaxation time of a fused quartz rod was measured at room temperature with fully digital excitation and detection.

Evolution of Clay Morphology in Polypropylene/Montmorillonite Nanocomposites upon Equi-biaxial Stretching: A Solid-State NMR and TEM Approach

Solid-state NMR and TEM were used to quantitatively examine the evolution of clay morphology upon equibiaxial stretching of polypropylene/montmorillonite (PP-MMT) nanocomposites up to a stretch ratio (?= final length/initial length) of 3.5. 1 H spin-lattice relaxation times were measured by the saturation-recovery sequence. For the nanocomposites, initial portions of the magnetization recovery
curves (e~20 ms) were found to depend on v t, indicative of diffusion-limited relaxation and in agreement with calculations based on estimates of the spin-diffusion barrier radius surrounding the paramagnetic centers in the clay, the electron-nucleus coupling constant, and the spin-diffusion coefficient. Initial slopes of these magnetization recovery curves directly correlated with the fraction of clay/polymer interface. New clay surface was exposed as a near linear function of strain. Long-time portions of the magnetization recovery curves yielded information on the average interparticle separations, which decreased slowly before reaching a plateau at ?=~2.5 as particles aligned. TEM images supported these findings and were used to define and quantify degrees of exfoliation and homogeneity from the NMR data. Exfoliation, defined as (platelets/ stack)-1, increased from 0.38 (unstretched) to 0.80 at ? = 3.5 for PP-MMT nanocomposites stretched at
150 C and 16 s-1. A lower stretch temperature, 145 C, which is slightly below melting onset, led to an exfoliation degree of 0.87 at ?= 2.8, consistent with the ability of higher melt viscosities to allow for higher shear stress transfer. Exposure of new clay surface is attributed to aggregate breakup and orientation at low strains (? e ~2) and to platelets sliding apart at higher strains.

Integrated data acquisition and processing to determine metabolite contents, relaxation times, and macromolecule baseline in single examinations of individual subjects

Absolute quantitation of clinical (1)H-MR spectra is virtually always incomplete for single subjects because the separate determination of spectrum, baseline, and transverse and longitudinal relaxation times in single subjects is prohibitively long. Integrated Processing and Acquisition of Data (IPAD) based on a combined 2-dimensional experimental and fitting strategy is suggested to substantially improve the information content from a given measurement time. A series of localized saturation-recovery spectra was recorded and combined with 2-dimensional prior-knowledge fitting to simultaneously determine metabolite T(1) (from analysis of the saturation-recovery time course), metabolite T(2) (from lineshape analysis based on metabolite and water peak shapes), macromolecular baseline (based on T(1) differences and analysis of the saturation-recovery time course), and metabolite concentrations (using prior knowledge fitting and conventional procedures of absolute standardization). The procedure was tested on metabolite solutions and applied in 25 subjects (15-78 years old). Metabolite content was comparable to previously found values. Interindividual variation was larger than intraindividual variation in repeated spectra for metabolite content as well as for some relaxation times. Relaxation times were different for various metabolite groups. Parts of the interindividual variation could be explained by significant age dependence of relaxation times.

Characterization of the macromolecule baseline in localized (1)H-MR spectra of human brain

Short-echo-time magnetic resonance spectra of human brain contain broad contributions from macromolecules. As they are a priori of unknown shape and intensity, they pose a problem if one wants to quantitate the overlying spectral features from low-molecular-weight metabolites. On the other hand, the macromolecular contributions may provide relevant clinical information themselves, if properly evaluated. Several methods, based on T(1), T(2), or spectral shape, have previously been suggested to suppress or edit the macromolecule contributions. Here, a method is presented based on a series of saturation recovery scans and that allows for simultaneous recording of the macromolecular baseline and the fully relaxed metabolite spectrum. In comparison to an inversion recovery technique aimed at nulling signals from long-T(1) components, the saturation recovery method is less susceptible to T(1) differences inherent in signals from different metabolites or introduced by pathology. The saturation recovery method was used to quantitate the macromolecular baseline in white and/or gray matter locations of the human brain in 40 subjects. It was found that the content and composition of MR visible macromolecules depends on cerebral location, as well as the age of the investigated subject, while no gender dependence could be found.

Error recovery in cyberphysical digital microfluidic biochips

Droplet-based digital microfluidics technology has now come of age, and software-controlled biochips for healthcare applications are starting to emerge. However, today's digital microfluidic biochips suffer from the drawback that there is no feedback to the control software from the underlying hardware platform. Due to the lack of precision inherent in biochemical experiments, errors are likely during droplet manipulation; error recovery based on the repetition of experiments leads to wastage of expensive reagents and hard-to-prepare samples. By exploiting recent advances in the integration of optical detectors (sensors) into a digital microfluidics biochip, we present a physical-aware system reconfiguration technique that uses sensor data at intermediate checkpoints to dynamically reconfigure the biochip. A cyberphysical resynthesis technique is used to recompute electrode-actuation sequences, thereby deriving new schedules, module placement, and droplet routing pathways, with minimum impact on the time-to-response. © 2012 IEEE.

Cold water immersion enhances recovery of submaximal muscle function after resistance exercise

We investigated the effect of cold water immersion (CWI) on the recovery of muscle function and physiological responses following high-intensity resistance exercise. Using a randomized, cross-over design, 10 physically active men performed high-intensity resistance exercise, followed by one of two recovery interventions: 10 min of cold water immersion at 10°C, or 10 min active recovery (low-intensity cycling). After the recovery interventions, maximal muscle function was assessed after 2 h and 4 h by measuring jump height and isometric squat strength. Submaximal muscle function was assessed after 6 h by measuring the average load lifted during six sets of 10 squats at 80% 1RM. Intramuscular temperature (1 cm) was also recorded, and venous blood samples were analyzed for markers of metabolism, vasoconstriction and muscle damage. CWI did not enhance recovery of maximal muscle function. However, during the final three sets of the submaximal muscle function test, the participants lifted a greater load (p<0.05; 38%; Cohen’s d 1.3) following CWI compared with active recovery. During CWI, muscle temperature decreased 6°C below post-exercise values, and remained below pre-exercise values for another 35 min. Venous blood O2 saturation decreased below pre-exercise values for 1.5 h after CWI. Serum endothelin-1 concentration did not change after CWI, whereas it decreased after active recovery. Plasma myoglobin concentration was lower, whereas plasma interleukin-6 concentration was higher after CWI compared with active recovery. These results suggest that cold water immersion after resistance exercise allow athletes to complete more work during subsequent training sessions, which could enhance long-term training adaptations.

Building resilient communities: Creating effective multi-channel communication during disaster response and recovery

Our aim is to examine evidence-based strategies to motivate appropriate action and increase informed decision-making during the response and recovery phases of disasters. We combine expertise in communication, consumer psychology and marketing, disaster and emergency management, and law. This poster presents findings from a social media work package, and preliminary findings from the focus group work package on emergency warning message comprehension.

A versatile and flexible digital pulse programmer for pulsed nuclear magnetic resonance

A versatile and flexible digital pulse programmer for two-pulse, three-pulse, saturation burst and Carr-Purcell sequences is described. Independently variable controls for pulse widths (0.2 mu s to 100 mu s), delay between pulses (0.2 mu s to 100 s) and for number of pulses (1 to 99) for the saturation burst and for the Carr-Purcell sequence, are brought to the front panel. The programmer can be used for one-shot experiments as well as for repetitive experiments.

headspace Digital Art Exhibition

headspace Digital Art Exhibition is a curated collection of artwork created during a youth arts project and research in which young people’s improved mental health wellbeing and mental health literacy were the focused outcomes for the project. The project aimed to improve mental health literacy, and offer greater opportunities for creative expression supporting young people facing mental health challenges. The Inside project aimed to build dialogue related to youth, arts, mental illness and recovery, through a partnership approach. The partnership approach involved artists and health workers in two separate headspace youth mental health services and aimed to provide opportunities to explore the potential of an arts and health framework. The project ran over ten weeks at both centres, incorporating themed activities such as unleashing inner selfie (sketching, photography and digital manipulation); creating dioramas (found object, three dimensional modelling); creating avatars (sculptural and digital animation); and digital narrating and poster creation (visual, written and spoken texts). Two professional artists facilitated the project, one in each location alongside headspace health workers at weekly workshops. A research component explored the appreciation of how artsbased workshops can be used alongside more traditional responses in youth specific mental health services. Both headspace centres had previously provided unstructured art activities as a way to showcase their services to young people, increase access, and to create a welcoming ‘safe’ youth friendly environment. However, these activities were generally extemporaneous and not specifically evaluated. The digital art exhibition collectively shares the artwork created by the young people and reveals the inter-relationships between risk and resilience and overcoming the odds. Inside unleashed possibilities for a sense of well-being and even happiness into the future.

A novel fiber-coated strong base-type anion exchanger with superfast kinetics. Removal and recovery of silver thiosulfate from aqueous solutions

A commercial acrylic fiber with 92% (w/w) acrylonitrile content was partially hydrolyzed converting a fraction of the nitrile (-CN) groups to carboxylic acid (-COOH) groups, to coat the fiber with polyethylenimine (PEI) resin, which was then crosslinked with glutaraldehyde and further quaternized with ethyl chloroacetate to produce a novel strong-base anionic exchanger in the form of fiber. Designated as PAN(QPEI.XG)(Cl-), the fibrous sorbent was compared with a commercial bead-form resin Amberlite IRA-458(Cl-) in respect of sorption capacity, selectivity, and kinetics for removal of silver thiosulfate complexes from aqueous solutions. Though the saturation level of [Ag(S2O3)(2)](3-) on PAN(QPEI.XG)(Cl-) is considerably less than that on IRA-458(Cl-), the gel-coated fibrous sorbent exhibits, as compared to the bead-form sorbent, a significantly higher sorption selectivity for the silver thiosulfate complex in the presence of excess of other anions Such as S2O32-, SO42-, and Cl-, and a remarkably faster rate of both sorption and stripping. The initial uptake of the sorbate by the fibrous sorbent is nearly instantaneous, reaching up to similar to 80% of the saturation capacity within 10 s, as compared to only similar to 12% on the bead-form sorbent. The high initial rate of uptake fits a shell-core kinetic model for sorption on fiber of cylindrical geometry. With 4M HCl, the stripping of the sorbed silver complex from the fibrous sorbent is clean and nearly instantaneous, while, in contrast, a much slower rate of stripping on the bead-form sorbent leads to its fouling due to a slow decomposition of the silver thiosulfate complex in the acidic medium.

Modelagem e simulação do escoamento imiscível em meios porosos fractais descritos pela equação de Kozeny-Carman Generalizada

O presente trabalho trata do escoamento bifásico em meios porosos heterogêneos de natureza fractal, onde os fluidos são considerados imiscíveis. Os meios porosos são modelados pela equação de Kozeny-Carman Generalizada (KCG), a qual relaciona a porosidade com a permeabilidade do meio através de uma nova lei de potência. Esta equação proposta por nós é capaz de generalizar diferentes modelos existentes na literatura e, portanto, é de uso mais geral. O simulador numérico desenvolvido aqui emprega métodos de diferenças finitas. A evolução temporal é baseada em um esquema de separação de operadores que segue a estratégia clássica chamada de IMPES. Assim, o campo de pressão é calculado implicitamente, enquanto que a equação da saturação da fase molhante é resolvida explicitamente em cada nível de tempo. O método de otimização denominado de DFSANE é utilizado para resolver a equação da pressão. Enfatizamos que o DFSANE nunca foi usado antes no contexto de simulação de reservatórios. Portanto, o seu uso aqui é sem precedentes. Para minimizar difusões numéricas, a equação da saturação é discretizada por um esquema do tipo "upwind", comumente empregado em simuladores numéricos para a recuperação de petróleo, o qual é resolvido explicitamente pelo método Runge-Kutta de quarta ordem. Os resultados das simulações são bastante satisfatórios. De fato, tais resultados mostram que o modelo KCG é capaz de gerar meios porosos heterogêneos, cujas características permitem a captura de fenômenos físicos que, geralmente, são de difícil acesso para muitos simuladores em diferenças finitas clássicas, como o chamado fenômeno de dedilhamento, que ocorre quando a razão de mobilidade (entre as fases fluidas) assume valores adversos. Em todas as simulações apresentadas aqui, consideramos que o problema imiscível é bidimensional, sendo, portanto, o meio poroso caracterizado por campos de permeabilidade e de porosidade definidos em regiões Euclideanas. No entanto, a teoria abordada neste trabalho não impõe restrições para sua aplicação aos problemas tridimensionais.

Visibility recovery on images acquired in attenuating media. Application to underwater, fog, and mammographic imaging

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Avaliação do possível impacto das técnicas de MEOR (Microbial Enhanced Oil Recovery) no fator de recuperação das reservas de petróleo e gás do Brasil

Os métodos tradicionais de estimular a produção de petróleo, envolvendo a injeção de água, vapor, gás ou outros produtos, estabeleceram a base conceitual para novos métodos de extração de óleo, utilizando micro-organismos e processos biológicos. As tecnologias que empregam os processos de bioestimulação e bioaumentação já são amplamente utilizadas em inúmeras aplicações industriais, farmacêuticas e agroindustriais, e mais recentemente, na indústria do petróleo. Dada a enorme dimensão econômica da indústria do petróleo, qualquer tecnologia que possa aumentar a produção ou o fator de recuperação de um campo petrolífero gera a expectativa de grandes benefícios técnicos, econômicos e estratégicos. Buscando avaliar o possível impacto de MEOR (microbial enhanced oil recovery) no fator de recuperação das reservas de óleo e gás no Brasil, e quais técnicas poderiam ser mais indicadas, foi feito um amplo estudo dessas técnicas e de diversos aspectos da geologia no Brasil. Também foram realizados estudos preliminares de uma técnica de MEOR (bioacidificação) com possível aplicabilidade em reservatórios brasileiros. Os resultados demonstram que as técnicas de MEOR podem ser eficazes na produção, solubilização, emulsificação ou transformação de diversos compostos, e que podem promover outros efeitos físicos no óleo ou na matriz da rocha reservatório. Também foram identificadas bacias petrolíferas brasileiras e recursos não convencionais com maior potencial para utilização de determinadas técnicas de MEOR. Finalmente, foram identificadas algumas técnicas de MEOR que merecem maiores estudos, entre as técnicas mais consolidadas (como a produção de biossurfatantes e biopolímeros, e o controle da biocorrosão), e as que ainda não foram completamente viabilizadas (como a gaseificação de carvão, óleo e matéria orgânica; a dissociação microbiana de hidratos de gás; a bioconversão de CO2 em metano; e a bioacidificação). Apesar de seu potencial ainda não ser amplamente reconhecido, as técnicas de MEOR representam o limiar de uma nova era na estimulação da produção de recursos petrolíferos existentes, e até mesmo para os planos de desenvolvimento de novas áreas petrolíferas e recursos energéticos. Este trabalho fornece o embasamento técnico para sugerir novas iniciativas, reconhecer o potencial estratégico de MEOR, e para ajudar a realizar seu pleno potencial e seus benefícios.

Biossorção de lantânio por Sargassum sp.: ensaios em batelada e contínuos

Diante dos avanços tecnológicos, pesquisadores têm intensificado a busca por métodos de remoção de metais, que tragam bons resultados de captação a partir de efluentes contaminados, aliados a um baixo custo. A utilização de materiais biológicos como algas marinhas, fungos e bactérias vem se destacando e se tornando uma solução atrativa quando comparados com os tratamentos químicos convencionais; essa técnica é denominada biossorção. A biossorção é um processo de captação de íons metálicos de uma solução, a partir de interações entre o metal e determinados sítios ativos presentes na parede celular da biomassa. Existe também um crescente interesse pelo estudo dos elementos de terras raras (TR) por possuirem alto valor agregado, acarretado por processos caros e de alta complexidade na sua separação e purificação. Desta forma, este trabalho teve como objetivo descrever o potencial de biossorção de lantânio - um representante dos TR - pela macroalga Sargassum sp., a partir de soluções aquosas. Para isso foram realizados estudos em batelada, aplicando modelos cinéticos e de equilíbrio, e estudos em regime contínuo de biossorção dos íons de lantânio (III), além de um sistema contínuo bimetálico, no qual houve a adição do metal cério, outro TR. As determinações analíticas foram realizadas por espectrometria de emissão ótica por plasma indutivamente acoplado. Os ensaios cinéticos foram realizados nas concentrações metálicas de 10 e 100 mg.L-1 e em duas concentrações distintas de biomassa 2 e 5 g.L-1 na temperatura de 301C. Dois modelos cinéticos foram testados, pseudo-primeira ordem e segunda ordem, tendo o modelo de segunda ordem apresentado melhor ajuste dos dados, com r2 igual a 0,9697. No ensaio de equilíbrio foi construída a isoterma que apresentou um perfil crescente na captação no entanto não alcançou a remoção máxima. Os modelos de Langmuir e Freundlich foram utilizados para ajustar os dados da isoterma, sendo verificado maior correlação dos dados com o modelo de Langmuir; resultando num valor de captação máxima calculado pelo modelo de 3,55 mmol.g-1. No ensaio dinâmico foram realizados dois experimentos, 1 e 2. O Experimento 1 foi realizado com três colunas interligadas e recheadas com 20g de biomassa cada, sendo bombeada uma solução aquosa de lantânio na concentração de 1,41mmol.L-1. O Experimento 2 foi constituido de uma solução contendo lantânio e cério ambos na mesma concentração anterior de 1,41 mmol.L-1, sendo bombeada somente para uma única coluna recheada com 20g de biomassa. Os resultados demonstraram que o ponto de saturação não foi atingido dentro das 8 horas em que se deu o processo, o que indica a alta afinidade da Sargassum sp. pelo lantânio e que a presença do cério associada a redução da vazão prejudicou a captação do lantânio

Bias-dependent recovery time of all-optical resonant nonlinearity in InGaAsP/InGaAsP MQW waveguide

We have investigated a resonant refractive nonlinearity in a semiconductor waveguide by measuring intensity dependent phase shifts and bias-dependent recovery times. The measurements were performed on an optimized 750-μm-long AR coated buried heterostructure MQW p-i-n waveguide with a bandedge at 1.48 μm. Figure 1 shows the experimental arrangement. The mode-locked color center laser was tuned to 50 meV beyond the bandedge and 8 ps pulses with peak incident power up to 57 W were coupled into the waveguide. Some residual bandtail absorption remains at this wavelength and this is sufficient to cause carriers to be photogenerated and these give rise to a refractive nonlinearity, predominantly by plasma and bandfilling effects. A Fabry-Perot interferometer is used to measure the spectrum of the light which exits the waveguide. The nonlinearity within the guide causes self phase modulation (SPM) of the light and a study of the spectrum allows information to be recovered on the magnitude and recovery time of the nonlinear phase shift with a reasonable degree of accuracy. SPM spectra were recorded for a variety of pulse energies coupled into he unbiased waveguide. Figure 2 shows the resultant phase shift measured from the SPM spectra as a function of pulse energy. The relationship is a linear one, indicating that no saturation of the nonlinearity occurs for coupled pulse energies up to 230 pJ. A π phase shift, the minimum necessary for an all-optical switch, is obtained for a coupled pulse energy of 57 pJ while the maximum phase shift, 4 π, was measured for 230 pJ. The SPM spectra were highly asymmetric with pulse energy shifted to higher frequencies. Such spectra are characteristic of a slow, negative nonlinearity. This relatively slow speed is expected for the unbiased guide as the recovery time will be of the order of the recombination time of the photogenerated electrons, about 1 ns for InGaAsP material. In order to reduce the recovery time of the nonlinearity, it is necessary to remove the photogenerated carriers from the waveguide by a process other than recombination. One such technique is to apply a reverse bias to the waveguide in order to sweep the carriers out. Figure 3 shows the effect on the recovery time of the nonlinearity of applying reverse bias to the waveguide for 230 pJ coupled power. The recovery time was reduced from one much longer than the length of the pulse, estimated to be about 1 ns, at zero bias to 18 ± 3 ps for a bias voltage greater than -4 V. This compares with a value of 24 ps obtained in a bulk waveguide.