Allergen motifs and the prediction of allergenicity

We have recently shown that the majority of allergens can be represented by allergen motifs. This observation prompted us to experimentally investigate the synthesized peptides corresponding to the in silico motifs with regard to potential IgE binding and cross-reactions with allergens. Two motifs were selected as examples to conduct in vitro studies. From the first motif, derived from allergenic MnSOD sequences, the motif stretch of the allergen Asp f 6 was selected and synthesized as a peptide (MnSOD Mot). The corresponding full-length MnSOD was also expressed in Escherichia coli and both were compared for IgE reactivity with sera of patients reacting to the MnSOD of Aspergillus fumigatus or Malassezia sympodialis. For the second motif, the invertebrate tropomyosin sequences were aligned and a motif consensus sequence was expressed as a recombinant protein (Trop Mot). The IgE reactivity of Trop Mot was analyzed in ELISA and compared to that of recombinant tropomyosin from the shrimp Penaeus aztecus (rPen a 1) in ImmunoCAP. MnSOD Mot was weakly recognized by some of the tested sera, suggesting that the IgE binding epitopes of a multimeric globular protein such as MnSOD cannot be fully represented by a motif peptide. In contrast, the motif Trop Mot showed the same IgE reactivity as shrimp full-length tropomyosin, indicating that the major allergenic reactivity of a repetitive structure such as tropomyosin can be covered by a motif peptide. Our results suggest that the motif-generating algorithm may be used for identifying major IgE binding structures of coiled-coil proteins.

Abciximab for thrombolysis during intracranial aneurysm coiling

INTRODUCTION: Thrombotic events are a common and severe complication of endovascular aneurysm treatment with significant impact on patients' outcome. This study evaluates risk factors for thrombus formation and assesses the efficacy and safety of abciximab for clot dissolution. MATERIALS AND METHODS: All patients treated with abciximab during (41 patients) or shortly after (22 patients) intracranial aneurysm coil embolisation were retrieved from the institutional database (2000 to 2007, 1,250 patients). Sixty-three patients (mean age, 55.3 years, +/-12.8) had received either intra-arterial or intravenous abciximab. Risk factors for clot formation were assessed and the angiographic and clinical outcome evaluated. RESULTS: No aneurysm rupture occurred during or after abciximab application. The intra-procedural rate of total recanalisation was 68.3%. Thromboembolic complications were frequently found in aneurysms of the Acom complex and of the basilar artery, whilst internal carotid artery aneurysms were underrepresented. Two patients died of treatment-related intracranial haemorrhages into preexisting cerebral infarcts. Two patients developed a symptomatic groin haematoma. CONCLUSIONS: Abciximab is efficacious and safe for thrombolysis during and after endovascular intracranial aneurysm treatment in the absence of preexisting ischaemic stroke.

Multimodality Preoperative Planning and Postoperative Follow-up of a Hybrid Cardiac Intervention

We describe the case of a 59-year-old man who had aortic regurgitation and a hypoplastic aortic valve and for whom an echocardiography evaluation revealed a vascular tumor in the roof of the left atrium, which was suspected to be a hemangioma. After undergoing preoperative invasive catheter coronary angiography, echocardiography, and multislice computed tomography examinations, the patient underwent an aortic miniroot replacement. Intraoperative findings confirmed the findings of the preoperative evaluations. The tumor, although macroscopically verified as a hemangioma, was not resected because of the tumor's position and size, and the threat of uncontrollable bleeding. After an uneventful postoperative clinical course, a subsequent successful transcatheter coil occlusion of the coronary fistula from the left circumflex coronary artery was performed as an alternative to surgical resection of the tumor. This case emphasizes the future role of a multimodality hybrid approach for diagnosis, planning (different 2- and 3-dimensional imaging modalities), and treatment in the form of combining interventional (transcatheter) and surgical (open heart) techniques, which could optimize different treatment strategies. This approach could be further improved by increasing the installations of hybrid operating rooms.

Shear band evolution in Zr/Hf-based bulk metallic glasses under static and dynamic indentations

Bulk metallic glasses (BMGs) exhibit superior mechanical properties as compared with other conventional materials and have been proposed for numerous engineering and technological applications. Zr/Hf-based BMGs or tungsten reinforced BMG composites are considered as a potential replacement for depleted uranium armor-piercing projectiles because of their ability to form localized shear bands during impact, which has been known to be the dominant plastic deformation mechanism in BMGs. However, in conventional tensile, compressive and bending tests, limited ductility has been observed because of fracture initiation immediately following the shear band formation. To fully investigate shear band characteristics, indentation tests that can confine the deformation in a limited region have been pursued. In this thesis, a detailed investigation of thermal stability and mechanical deformation behavior of Zr/Hf-based BMGs is conducted. First, systematic studies had been implemented to understand the influence of relative compositions of Zr and Hf on thermal stability and mechanical property evolution. Second, shear band evolution under indentations were investigated experimentally and theoretically. Three kinds of indentation studies were conducted on BMGs in the current study. (a) Nano-indentation to determine the mechanical properties as a function of Hf/Zr content. (b) Static Vickers indentation on bonded split specimens to investigate the shear band evolution characteristics beneath the indention. (c) Dynamic Vickers indentation on bonded split specimens to investigate the influence of strain rate. It was found in the present work that gradually replacing Zr by Hf remarkably increases the density and improves the mechanical properties. However, a slight decrease in glass forming ability with increasing Hf content has also been identified through thermodynamic analysis although all the materials in the current study were still found to be amorphous. Many indentation studies have revealed only a few shear bands surrounding the indent on the top surface of the specimen. This small number of shear bands cannot account for the large plastic deformation beneath the indentations. Therefore, a bonded interface technique has been used to observe the slip-steps due to shear band evolution. Vickers indentations were performed along the interface of the bonded split specimen at increasing loads. At small indentation loads, the plastic deformation was primarily accommodated by semi-circular primary shear bands surrounding the indentation. At higher loads, secondary and tertiary shear bands were formed inside this plastic zone. A modified expanding cavity model was then used to predict the plastic zone size characterized by the shear bands and to identify the stress components responsible for the evolution of the various types of shear bands. The applicability of various hardness—yield-strength ( H −σγ ) relationships currently available in the literature for bulk metallic glasses (BMGs) is also investigated. Experimental data generated on ZrHf-based BMGs in the current study and those available elsewhere on other BMG compositions were used to validate the models. A modified expanding-cavity model, employed in earlier work, was extended to propose a new H −σγ relationship. Unlike previous models, the proposed model takes into account not only the indenter geometry and the material properties, but also the pressure sensitivity index of the BMGs. The influence of various model parameters is systematically analyzed. It is shown that there is a good correlation between the model predictions and the experimental data for a wide range of BMG compositions. Under dynamic Vickers indentation, a decrease in indentation hardness at high loading rate was observed compared to static indentation hardness. It was observed that at equivalent loads, dynamic indentations produced more severe deformation features on the loading surface than static indentations. Different from static indentation, two sets of widely spaced semi-circular shear bands with two different curvatures were observed. The observed shear band pattern and the strain rate softening in indentation hardness were rationalized based on the variations in the normal stress on the slip plane, the strain rate of shear and the temperature rise associated with the indentation deformation. Finally, a coupled thermo-mechanical model is proposed that utilizes a momentum diffusion mechanism for the growth and evolution of the final spacing of shear bands. The influence of strain rate, confinement pressure and critical shear displacement on the shear band spacing, temperature rise within the shear band, and the associated variation in flow stress have been captured and analyzed. Consistent with the known pressure sensitive behavior of BMGs, the current model clearly captures the influence of the normal stress in the formation of shear bands. The normal stress not only reduces the time to reach critical shear displacement but also causes a significant temperature rise during the shear band formation. Based on this observation, the variation of shear band spacing in a typical dynamic indentation test has been rationalized. The temperature rise within a shear band can be in excess of 2000K at high strain rate and high confinement pressure conditions. The associated drop in viscosity and flow stress may explain the observed decrease in fracture strength and indentation hardness. The above investigations provide valuable insight into the deformation behavior of BMGs under static and dynamic loading conditions. The shear band patterns observed in the above indentation studies can be helpful to understand and model the deformation features under complex loading scenarios such as the interaction of a penetrator with armor. Future work encompasses (1) extending and modifying the coupled thermo-mechanical model to account for the temperature rise in quasistatic deformation; and (2) expanding this model to account for the microstructural variation-crystallization and free volume migration associated with the deformation.

Energy harvesting from body motion using rotational micro-generation

Autonomous system applications are typically limited by the power supply operational lifetime when battery replacement is difficult or costly. A trade-off between battery size and battery life is usually calculated to determine the device capability and lifespan. As a result, energy harvesting research has gained importance as society searches for alternative energy sources for power generation. For instance, energy harvesting has been a proven alternative for powering solar-based calculators and self-winding wristwatches. Thus, the use of energy harvesting technology can make it possible to assist or replace batteries for portable, wearable, or surgically-implantable autonomous systems. Applications such as cardiac pacemakers or electrical stimulation applications can benefit from this approach since the number of surgeries for battery replacement can be reduced or eliminated. Research on energy scavenging from body motion has been investigated to evaluate the feasibility of powering wearable or implantable systems. Energy from walking has been previously extracted using generators placed on shoes, backpacks, and knee braces while producing power levels ranging from milliwatts to watts. The research presented in this paper examines the available power from walking and running at several body locations. The ankle, knee, hip, chest, wrist, elbow, upper arm, side of the head, and back of the head were the chosen target localizations. Joints were preferred since they experience the most drastic acceleration changes. For this, a motor-driven treadmill test was performed on 11 healthy individuals at several walking (1-4 mph) and running (2-5 mph) speeds. The treadmill test provided the acceleration magnitudes from the listed body locations. Power can be estimated from the treadmill evaluation since it is proportional to the acceleration and frequency of occurrence. Available power output from walking was determined to be greater than 1mW/cm³ for most body locations while being over 10mW/cm³ at the foot and ankle locations. Available power from running was found to be almost 10 times higher than that from walking. Most energy harvester topologies use linear generator approaches that are well suited to fixed-frequency vibrations with sub-millimeter amplitude oscillations. In contrast, body motion is characterized with a wide frequency spectrum and larger amplitudes. A generator prototype based on self-winding wristwatches is deemed to be appropriate for harvesting body motion since it is not limited to operate at fixed-frequencies or restricted displacements. Electromagnetic generation is typically favored because of its slightly higher power output per unit volume. Then, a nonharmonic oscillating rotational energy scavenger prototype is proposed to harness body motion. The electromagnetic generator follows the approach from small wind turbine designs that overcome the lack of a gearbox by using a larger number of coil and magnets arrangements. The device presented here is composed of a rotor with multiple-pole permanent magnets having an eccentric weight and a stator composed of stacked planar coils. The rotor oscillations induce a voltage on the planar coil due to the eccentric mass unbalance produced by body motion. A meso-scale prototype device was then built and evaluated for energy generation. The meso-scale casing and rotor were constructed on PMMA with the help of a CNC mill machine. Commercially available discrete magnets were encased in a 25mm rotor. Commercial copper-coated polyimide film was employed to manufacture the planar coils using MEMS fabrication processes. Jewel bearings were used to finalize the arrangement. The prototypes were also tested at the listed body locations. A meso-scale generator with a 2-layer coil was capable to extract up to 234 µW of power at the ankle while walking at 3mph with a 2cm³ prototype for a power density of 117 µW/cm³. This dissertation presents the analysis of available power from walking and running at different speeds and the development of an unobtrusive miniature energy harvesting generator for body motion. Power generation indicates the possibility of powering devices by extracting energy from body motion.

Advanced morphological and biochemical magnetic resonance imaging of cartilage repair procedures in the knee joint at 3 Tesla

Morphological and biochemical magnetic resonance imaging (MRI) is due to high field MR systems, advanced coil technology, and sophisticated sequence protocols capable of visualizing articular cartilage in vivo with high resolution in clinical applicable scan time. Several conventional two-dimensional (2D) and three-dimensional (3D) approaches show changes in cartilage structure. Furthermore newer isotropic 3D sequences show great promise in improving cartilage imaging and additionally in diagnosing surrounding pathologies within the knee joint. Functional MR approaches are additionally able to provide a specific measure of the composition of cartilage. Cartilage physiology and ultra-structure can be determined, changes in cartilage macromolecules can be detected, and cartilage repair tissue can thus be assessed and potentially differentiated. In cartilage defects and following nonsurgical and surgical cartilage repair, morphological MRI provides the basis for diagnosis and follow-up evaluation, whereas biochemical MRI provides a deeper insight into the composition of cartilage and cartilage repair tissue. A combination of both, together with clinical evaluation, may represent a desirable multimodal approach in the future, also available in routine clinical use.

In vivo biochemical 7.0 Tesla magnetic resonance: preliminary results of dGEMRIC, zonal T2, and T2* mapping of articular cartilage

INTRODUCTION: Ultra-high-field whole-body systems (7.0 T) have a high potential for future human in vivo magnetic resonance imaging (MRI). In musculoskeletal MRI, biochemical imaging of articular cartilage may benefit, in particular. Delayed gadolinium-enhanced MRI of cartilage (dGEMRIC) and T2 mapping have shown potential at 3.0 T. Although dGEMRIC, allows the determination of the glycosaminoglycan content of articular cartilage, T2 mapping is a promising tool for the evaluation of water and collagen content. In addition, the evaluation of zonal variation, based on tissue anisotropy, provides an indicator of the nature of cartilage ie, hyaline or hyaline-like articular cartilage.Thus, the aim of our study was to show the feasibility of in vivo dGEMRIC, and T2 and T2* relaxation measurements, at 7.0 T MRI; and to evaluate the potential of T2 and T2* measurements in an initial patient study after matrix-associated autologous chondrocyte transplantation (MACT) in the knee. MATERIALS AND METHODS: MRI was performed on a whole-body 7.0 T MR scanner using a dedicated circular polarization knee coil. The protocol consisted of an inversion recovery sequence for dGEMRIC, a multiecho spin-echo sequence for standard T2 mapping, a gradient-echo sequence for T2* mapping and a morphologic PD SPACE sequence. Twelve healthy volunteers (mean age, 26.7 +/- 3.4 years) and 4 patients (mean age, 38.0 +/- 14.0 years) were enrolled 29.5 +/- 15.1 months after MACT. For dGEMRIC, 5 healthy volunteers (mean age, 32.4 +/- 11.2 years) were included. T1 maps were calculated using a nonlinear, 2-parameter, least squares fit analysis. Using a region-of-interest analysis, mean cartilage relaxation rate was determined as T1 (0) for precontrast measurements and T1 (Gd) for postcontrast gadopentate dimeglumine [Gd-DTPA(2-)] measurements. T2 and T2* maps were obtained using a pixelwise, monoexponential, non-negative least squares fit analysis; region-of-interest analysis was carried out for deep and superficial cartilage aspects. Statistical evaluation was performed by analyses of variance. RESULTS: Mean T1 (dGEMRIC) values for healthy volunteers showed slightly different results for femoral [T1 (0): 1259 +/- 277 ms; T1 (Gd): 683 +/- 141 ms] compared with tibial cartilage [T1 (0): 1093 +/- 281 ms; T1 (Gd): 769 +/- 150 ms]. Global mean T2 relaxation for healthy volunteers showed comparable results for femoral (T2: 56.3 +/- 15.2 ms; T2*: 19.7 +/- 6.4 ms) and patellar (T2: 54.6 +/- 13.0 ms; T2*: 19.6 +/- 5.2 ms) cartilage, but lower values for tibial cartilage (T2: 43.6 +/- 8.5 ms; T2*: 16.6 +/- 5.6 ms). All healthy cartilage sites showed a significant increase from deep to superficial cartilage (P < 0.001). Within healthy cartilage sites in MACT patients, adequate values could be found for T2 (56.6 +/- 13.2 ms) and T2* (18.6 +/- 5.3 ms), which also showed a significant stratification. Within cartilage repair tissue, global mean values showed no difference, with 55.9 +/- 4.9 ms for T2 and 16.2 +/- 6.3 ms for T2*. However, zonal assessment showed only a slight and not significant increase from deep to superficial cartilage (T2: P = 0.174; T2*: P = 0.150). CONCLUSION: In vivo T1 dGEMRIC assessment in healthy cartilage, and T2 and T2* mapping in healthy and reparative articular cartilage, seems to be possible at 7.0 T MRI. For T2 and T2*, zonal variation of articular cartilage could also be evaluated at 7.0 T. This zonal assessment of deep and superficial cartilage aspects shows promising results for the differentiation of healthy and affected articular cartilage. In future studies, optimized protocol selection, and sophisticated coil technology, together with increased signal at ultra-high-field MRI, may lead to advanced biochemical cartilage imaging.

Kinematic biomechanical assessment of human articular cartilage transplants in the knee using 3-T MRI: an in vivo reproducibility study

The aims of this study were to examine the clinical feasibility and reproducibility of kinematic MR imaging with respect to changes in T (2) in the femoral condyle articular cartilage. We used a flexible knee coil, which allows acquisition of data in different positions from 40 degrees flexion to full extension during MR examinations. The reproducibility of T (2) measurements was evaluated for inter-rater and inter-individual variability and determined as a coefficient of variation (CV) for each volunteer and rater. Three different volunteers were measured twice and regions of interest (ROIs) were selected by three raters at different time points. To prove the clinical feasibility of this method, 20 subjects (10 patients and 10 age- and sex-matched volunteers) were enrolled in the study. Inter-rater variability ranged from 2 to 9 and from 2 to 10% in the deep and superficial zones, respectively. Mean inter-individual variability was 7% for both zones. Different T (2) values were observed in the superficial cartilage zone of patients compared with volunteers. Since repair tissue showed a different behavior in the contact zone compared with healthy cartilage, a possible marker for improved evaluation of repair tissue quality after matrix-associated autologous chondrocyte transplantation (MACT) may be available and may allow biomechanical assessment of cartilage transplants.

Fabrication and characterization of room temperature operating single electron transistors using focused ion beam technologies

The single electron transistor (SET) is a Coulomb blockade device, whose operation is based on the controlled manipulation of individual electrons. Single electron transistors show immense potential to be used in future ultra lowpower devices, high density memory and also in high precision electrometry. Most SET devices operate at cryogenic temperatures, because the charging energy is much smaller than the thermal oscillations. The room temperature operation of these devices is possible with sub- 10nm nano-islands due to the inverse dependance of charging energy on the radius of the conducting nano-island. The fabrication of sub-10nm features with existing lithographic techniques is a technological challenge. Here we present the results for the first room temperature operating SET device fabricated using Focused Ion Beam deposition technology. The SET device, incorporates an array of tungsten nano-islands with an average diameter of 8nm. The SET devices shows clear Coulomb blockade for different gate voltages at room temperature. The charging energy of the device was calculated to be 160.0 meV; the capacitance per junction was found to be 0.94 atto F; and the tunnel resistance per junction was calculated to be 1.26 G Ω. The tunnel resistance is five orders of magnitude larger than the quantum of resistance (26 k Ω) and allows for the localization of electrons on the tungsten nano-island. The lower capacitance of the device combined with the high tunnel resistance, allows for the Coulomb blockade effects observed at room temperature. Different device configurations, minimizing the total capacitance of the device have been explored. The effect of the geometry of the nano electrodes on the device characteristics has been presented. Simulated device characteristics, based on the soliton model have been discussed. The first application of SET device as a gas sensor has been demonstrated.

Subarachnoid hemorrhage and intracerebral hematoma: incidence, prognostic factors, and outcome

OBJECTIVE: To analyze the incidence and impact of an intracerebral hematoma (ICH) on treatment and outcome in patients with aneurysmal subarachnoid hemorrhage. METHODS: Data of 585 consecutive patients with subarachnoid hemorrhage from June 1999 to December 2005 were prospectively entered in a database. ICH was diagnosed and size was measured by computed tomographic scan before aneurysm occlusion. Fifty patients (8.5%) presented with an ICH larger than 50 cm3. The treatment decision (coil, clip, or hematoma evacuation) was based on an interdisciplinary approach. Patients were stratified into good (Hunt and Hess Grades I-III) versus poor (Hunt and Hess Grades IV and V) grade, and outcome was assessed according to the modified Rankin Scale at 6 months. RESULTS: Overall, 358 patients presented in good grade, with 4 of them having ICH (1.1%); and 227 patients presented in poor grade, with 46 of them having ICH (20.3%, P < 0.01). In good-grade patients with an ICH (n = 4), a favorable outcome (modified Rankin Scale score of 0-2) was achieved in 1 patient (25%), and in 246 patients (75%) without an ICH (P = 0.053; odds ratio, 0.11). A favorable outcome was achieved in 5 poor-grade patients (12.8%) with an ICH and in 40 patients (23.7%) without an ICH (P = 0.19; odds ratio, 0.47). Time to treatment was significantly shorter in patients with an ICH than without an ICH (median, 7 versus 26 h; P < 0.001) and shortest in patients with favorable outcome (3.5 hours; P < 0.01). CONCLUSION: The current data confirm that the presence of an ICH is a predictor of unfavorable outcome. However, despite large ICHs, a significant number of patients have a good outcome. To achieve a favorable outcome, ultra-early treatment with hematoma evacuation and aneurysm obliteration seems to be mandatory.

RISK OF SHUNT-DEPENDENT HYDROCEPHALUS AFTER OCCLUSION OF RUPTURED INTRACRANIAL ANEURYSMS BY SURGICAL CLIPPING OR ENDOVASCULAR COILING: A SINGLE-INSTITUTION SERIES AND META-ANALYSIS

OBJECTIVE: To compare the risk of shunt-dependent hydrocephalus after treatment of ruptured intracranial aneurysms by clipping versus coiling. METHODS: We analyzed 596 patients prospectively added to our database from July of 1999 to November of 2005 concerning the risk of shunt dependency after clipping versus coiling. Factors analyzed included age; sex; Hunt and Hess grade; Fisher grade; acute hydrocephalus; intraventricular hemorrhage; angiographic vasospasm; and number, size, and location of aneurysms. In addition, a meta-analysis of available data from the literature was performed identifying four studies with quantitative data on the frequency of clip, coil, and shunt dependency. RESULTS: The institutional series revealed Hunt and Hess grade, Fisher grade, acute hydrocephalus, intraventricular hemorrhage, and angiographic vasospasm as significant (P < 0.05) risk factors for shunt dependency after a univariate analysis. In a multivariate logistic regression analysis, we isolated intraventricular hemorrhage, acute hydrocephalus, and angiographic vasospasm as independent, significant risk factors for shunt dependency. The meta-analysis, including the current data, revealed a significantly higher risk for shunt dependency after coiling than after clipping (P = 0.01). CONCLUSION: Clipping of a ruptured aneurysm may be associated with a lower risk for developing shunt dependency, possibly by clot removal. This might influence long-term outcome and surgical decision making.

Adaptive control of sinusoidal brushless DC motor actuators

Electrical Power Assisted Steering system (EPAS) will likely be used on future automotive power steering systems. The sinusoidal brushless DC (BLDC) motor has been identified as one of the most suitable actuators for the EPAS application. Motor characteristic variations, which can be indicated by variations of the motor parameters such as the coil resistance and the torque constant, directly impart inaccuracies in the control scheme based on the nominal values of parameters and thus the whole system performance suffers. The motor controller must address the time-varying motor characteristics problem and maintain the performance in its long service life. In this dissertation, four adaptive control algorithms for brushless DC (BLDC) motors are explored. The first algorithm engages a simplified inverse dq-coordinate dynamics controller and solves for the parameter errors with the q-axis current (iq) feedback from several past sampling steps. The controller parameter values are updated by slow integration of the parameter errors. Improvement such as dynamic approximation, speed approximation and Gram-Schmidt orthonormalization are discussed for better estimation performance. The second algorithm is proposed to use both the d-axis current (id) and the q-axis current (iq) feedback for parameter estimation since id always accompanies iq. Stochastic conditions for unbiased estimation are shown through Monte Carlo simulations. Study of the first two adaptive algorithms indicates that the parameter estimation performance can be achieved by using more history data. The Extended Kalman Filter (EKF), a representative recursive estimation algorithm, is then investigated for the BLDC motor application. Simulation results validated the superior estimation performance with the EKF. However, the computation complexity and stability may be barriers for practical implementation of the EKF. The fourth algorithm is a model reference adaptive control (MRAC) that utilizes the desired motor characteristics as a reference model. Its stability is guaranteed by Lyapunov’s direct method. Simulation shows superior performance in terms of the convergence speed and current tracking. These algorithms are compared in closed loop simulation with an EPAS model and a motor speed control application. The MRAC is identified as the most promising candidate controller because of its combination of superior performance and low computational complexity. A BLDC motor controller developed with the dq-coordinate model cannot be implemented without several supplemental functions such as the coordinate transformation and a DC-to-AC current encoding scheme. A quasi-physical BLDC motor model is developed to study the practical implementation issues of the dq-coordinate control strategy, such as the initialization and rotor angle transducer resolution. This model can also be beneficial during first stage development in automotive BLDC motor applications.

Biological materials : Part A. tuning LCST of raft copolymers and gold/copolymer hybrid nanoparticles and Part B. biobased nanomaterials

The research described in this dissertation is comprised of two major parts. The first part studied the effects of asymmetric amphiphilic end groups on the thermo-response of diblock copolymers of (oligo/di(ethylene glycol) methyl ether (meth)acrylates, OEGA/DEGMA) and the hybrid nanoparticles of these copolymers with a gold nanoparticle core. Placing the more hydrophilic end group on the more hydrophilic block significantly increased the cloud point compared to a similar copolymer composition with the end group placement reversed. For a given composition, the cloud point was shifted by as much as 28 °C depending on the placement of end groups. This is a much stronger effect than either changing the hydrophilic/hydrophobic block ratio or replacing the hydrophilic acrylate monomer with the equivalent methacrylate monomer. The temperature range of the coil-globule transition was also altered. Binding these diblock copolymers to a gold core decreased the cloud point by 5-15 °C and narrowed the temperature range of the coil-globule transition. The effects were more pronounced when the gold core was bound to the less hydrophilic block. Given the limited numbers of monomers that are approved safe for in vivo use, employing amphiphilic end group placement is a useful tool to tune a thermo-response without otherwise changing the copolymer composition. The second part of the dissertation investigated the production of value-added nanomaterials from two biorefinery “wastes”: lignin and peptidoglycan. Different solvents and spinning methods (melt-, wet-, and electro-spinning) were tested to make lignin/cellulose blended and carbonized fibers. Only electro-spinning yielded fibers having a small enough diameter for efficient carbonization ( Peptidoglycan (a bacterial cell wall material) was copolymerized with poly-(3-hydroxybutyrate), a common polyhydroxyalkanoate produced by bacteria with the objective of determining if a useful material could be obtained with a less rigorous work-up on harvesting polyhydroxyalkanoates. The copolyesteramide product having 25 wt.% peptidoglycan from a highly purified peptidoglycan increased thermal stability by 100-200 °C compared to the poly-(3-hydroxybutyrate) control, while a less pure peptidoglycan, harvested from B. megaterium (ATCC 11561), gave a 25-50 °C increase in thermal stability. Both copolymers absorbed more moisture than pure poly-(3-hydroxybutyrate). The results suggest that a less rigorously harvested and purified polyhydroxyalkanoate might be useful for some applications.

Bacteriorhodopsin protein hybrids for chemical and biological sensing

Bacteriorhodopsin (bR), an optoelectric protein found in Halobacterium salinarum, has the potential for use in protein hybrid sensing systems. Bacteriorhodopsin has no intrinsic sensing properties, however molecular and chemical tools permit production of bR protein hybrids with transducing and sensing properties. As a proof of concept, a maltose binding protein-bacteriorhodopsin ([MBP]-bR) hybrid was developed. It was proposed that the energy associated with target molecule binding, maltose, to the hybrid sensor protein would provide a means to directly modulate the electrical output from the MBP-bR bio-nanosensor platform. The bR protein hybrid is produced by linkage between bR (principal component of purified purple membrane [PM]) and MBP, which was produced by use of a plasmid expression vector system in Escherichia coli and purified utilizing an amylose affinity column. These proteins were chemically linked using 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS), which facilitates formation of an amide bond between a primary carboxylic acid and a primary amine. The presence of novel protein hybrids after chemical linkage was analyzed by SDSPAGE. Soluble proteins (MBP-only derivatives and unlinked MBP) were separated from insoluble proteins (PM derivatives and unlinked PM) using size exclusion chromatography. The putatively identified MBP-bR protein hybrid, in addition to unlinked bR, was collected. This sample was normalized for bR concentration to native PM and both were deposited onto indium tin oxide (ITO) coated glass slides by electrophoretic sedimentation. The photoresponse of both samples, activated using 100 Watt tungsten lamp at 10 cm distance, were equal at 175 mV. Testing of deposited PM with 1 mM sucrose or 1 mM maltose showed no change in the photoresponse of the xiv material, however addition of 1 mM maltose to the deposited MBP-bR linked hybrid material elicited a 57% decrease in photoresponse indicating a positive response for targeting of maltose. This chemically linked MBP-bR hybrid protein, with bacteriorhodopsin, as a photoresponsive transducing substrate, shows promise for creation of a universal sensing array by attachment of other pertinent sensing materials, in lieu of the maltose binding protein utilized. This strategy would allow significant reduction in sensor size, while increasing responsiveness and sensitivity at nano and picomolar levels.

Wireless and passive pressure sensor system based on the magnetic higher-order harmonic field

The goal of this work is to develop a magnetic-based passive and wireless pressure sensor for use in biomedical applications. Structurally, the pressure sensor, referred to as the magneto-harmonic pressure sensor, is composed of two magnetic elements: a magnetically-soft material acts as a sensing element, and a magnetically hard material acts as a biasing element. Both elements are embedded within a rigid sensor body and sealed with an elastomer pressure membrane. Upon excitation of an externally applied AC magnetic field, the sensing element is capable of producing higher-order magnetic signature that is able to be remotely detected with an external receiving coil. When exposed to environment with changing ambient pressure, the elastomer pressure membrane of pressure sensor is deflected depending on the surrounding pressure. The deflection of elastomer membrane changes the separation distance between the sensing and biasing elements. As a result, the higher-order harmonic signal emitted by the magnetically-soft sensing element is shifted, allowing detection of pressure change by determining the extent of the harmonic shifting. The passive and wireless nature of the sensor is enabled with an external excitation and receiving system consisting of an excitation coil and a receiving coil. These unique characteristics made the sensor suitable to be used for continuous and long-term pressure monitoring, particularly useful for biomedical applications which often require frequent surveillance. In this work, abdominal aortic aneurysm is selected as the disease model for evaluation the performance of pressure sensor and system. Animal model, with subcutaneous sensor implantation in mice, was conducted to demonstrate the efficacy and feasibility of pressure sensor in biological environment.