Conformational Properties of Angiotensin II and Its Active and Inactive TOAC-Labeled Analogs in the Presence of Micelles. Electron Paramagnetic Resonance, Fluorescence, and Circular Dichroism Studies

The interaction between angiotensin II (AII, DRVYIHPF) and its analogs carrying 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid (TOAC) and detergents-negatively charged sodium dodecyl sulfate (SDS) and zwitterionic N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS)-was examined by means of EPR, CD, and fluorescence. EPR spectra of partially active TOAC(1)-AII and inactive TOAC(3)-AII in aqueous solution indicated fast tumbling, the freedom of motion being greater at the N-terminus. Line broadening occurred upon interaction with micelles. Below SDS critical micelle concentration, broader lines indicated complex formation with tighter molecular packing than in micelles. Small changes in hyperfine splittings evinced TOAC location at the micelle-water interface. The interaction with anionic micelles was more effective than with zwitterionic micelles. Peptide-micelle interaction caused fluorescence increase. The TOAC-promoted intramolecular fluorescence quenching was more, pronounced for TOAC(3)-AII because of the proximity between the nitroxide and Tyr(4). CD spectra showed that although both AII and TOAC(1)-AII presented flexible conformations in water, TOAC(3)-AII displayed conformational restriction because of the TOAC-imposed bend (Schreier et al., Biopolymers 2004, 74, 389). In HPS, conformational changes were observed for the labeled peptides at neutral and basic pH. In SDS, all peptides underwent pH-dependent conformational changes. Although the spectra suggested similar folds for All and TOAC(1)-AII, different conformations were acquired by TOAC(3)-AII. The membrane environment has been hypothesized to shift conformational equilibria so as to stabilize the receptor-bound conformation of ligands. The fact that TOAC(3)-AII is unable to acquire conformations similar to those of native AII and partially active TOAC(1)-AII is probably the explanation for its lack of biological activity. (C) 2009 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 92: 525-537, 2009.

Toward a broader appreciation of human motion in education

Motion is a fundamental activity for the healthy functioning human organism. Its importance, however, is increasingly de-valued in Western cultures as they speed toward adopting technologies and virtual experiences as adjuncts to, and even replacements for7 traditional educational structures and processes that involve physical activity. Organised and reflective experience of human motion is becoming increasingly marginalised in teaching methodologies and learning programs in educational institutions at all levels around the globe. This inquiry sets out to gain a greater understanding of why people and human motion become disconnected, particularly during periods of formal education. A central question and two sub-questions form the basis of the inquiry. The central question asks why human motion is not valued and more utilised in education. In particular, why do learning areas that directly represent involvement with human motion, such as physical education, continually struggle in education programs. It directs the investigation to focus on the causes rather than the symptoms of the disuse and devaluation of human motion in Australian education. The two sub-questions split the praxis of the study. The first seeks to understand how the causes of devaluation work in the educational context lo affect the lack of acknowledgement; and the second considers ways to counter the disuse of human movement in education programs. To address these questions, the research focuses on rebutting the notion of a mind-body dualism. Rather, it seeks to better understand how humans learn and function as monists - integrated beings, acquiring self-knowledge in their 'world of being' in which bodily and emotional experiences, and reasoning are inextricably intertwined. I have approached this qualitative research as an ethnographic sociologist examining the issues from a critical high modernist perspective in order to demonstrate the pervading influence in Australian education of strong beliefs and values from the era of Enlightenment. Narrative analysis of 'memoir' in the form of self-defining memories was selected to gain a sensibility of the connectedness between human emotion, motion and reasoning in the lived experiences of students in three primary and three secondary schools across Years 2-12. An opportunity for human movement to be more valued and utilised in emerging educational frameworks that have life knowledge, dispositions and capabilities at their core is identified. The inquiry proposes a conceptualisation of human motion in education for new times characterised by the need for people to develop personal resources and strong positive identities in order to cope with a world of rapid change and uncertainty.

Studies of natriuretic peptides in Tradescantia

The idea that plant development and physiological responses to the environment are governed largely by the five classical hormones is being superseded by the view that a much larger range of very different molecules also have such functions in plants. Recent evidence suggests that natriuretic peptides (NPs) known to function in vertebrates as regulators of salt and water balance may also play this role in plants. This thesis adds experimental results obtained in vitro and in situ that contribute to further establishing NPs as novel endogenous regulators in plants.

NMR and Raman studies of a novel fast-ion-conducting polymer-in-salt electrolyte based on LiCF3SO3 and PAN

We report spectroscopic results from investigations of a novel solid polymeric fast-ion-conductor based on poly(acrylonitrile), (PAN, of repeat unit [CH₂CH(CN)]_n), and the salt LiCF₃SO3 . From NMR studies of the temperature and concentration dependencies of ⁷Li- and ^lH-NMR linewidths, we conclude that significant ionic motion occurs at temperatures close to the glass transition temperature of these polymer-in-salt electrolytes, in accordance with a recent report on the ionic conductivity. In the dilute salt-in-polymer regime, however, ionic motion appears mainly to be confined to local salt-rich domains, as determined from the dramatic composition dependence of the ionic conductivity. FT-Raman spectroscopy is used to directly probe the local chemical anionic environment, as well as the Li⁺–PAN interaction. The characteristic δ_s(CF₃) mode of the CF₃SO₃⁻ anion at _~750–780 cm^−l shows that the ionic substructure is highly complex. Notably, no spectroscopic evidence of free anions is found even at relatively salt-depleted compositions (e.g. N:Li_~60–10:1). A strong Li⁺–PAN interaction is manifested as a pronounced shift of the characteristic polymer C=N stretching mode, found at _~2244 cm^−l in pure PAN, to _~2275 cm^−l for Li⁺-coordinated C=N moieties. Our proton-NMR data suggest that upon complexation of PAN with LiCF3 SO₃, the glass transition occurs at progressively lower temperatures.

Design earthquake ground motion prediction for Perth metropolitan area with microtremor measurements for site characterization

Perth is the largest city in Western Australia and home to three-quarters of the state's residents. In recent decades, there have been a lot of earthquake activities just east of Perth in an area known as the South-West Seismic Zone. Previous numerical results of site response analyses based on limited available geology information for PMA indicated that Perth Basin might amplify the bedrock motion by more than 10 times at some frequencies and at some sites. Hence, more detailed studies on site characterization and amplification are necessary. The microtremor method using spatial autocorrelation (SPAC) processing is a useful tool for gaining thickness and shear wave velocity (SWV) of sediments and has been adopted in many previous studies. In this study, the response spectrum of rock site corresponding to the 475-year return period for PMA is defined according to the probabilistic seismic hazard analysis (PSHA) based on the latest ground motion attenuation model of Southwest Western Australia. Site characterization in PMA is performed using two microtremor measurements, namely SPAC technique and H/V method. The clonal selection algorithm (CSA) is introduced to perform direct inversion of SPAC curves to determine the soil profiles of representative PMA sites investigated in this study. Using the simulated bedrock motion as input, the responses of the soil sites are estimated using numerical method based on the shear-wave velocity vs. depth profiles determined from the SPAC technique. The response spectrum of the earthquake ground motion on surface of each site is derived from the numerical results of the site response analysis, and compared with the respective design spectrum defined in the Australian Earthquake Loading Code. The comparison shows that the code spectra are conservative in the short period range, but may slightly underestimate the response spectrum at some long period range.

Toward automatic extraction of expressive elements from motion pictures : tempo

This paper addresses the challenge of bridging the semantic gap that exists between the simplicity of features that can be currently computed in automated content indexing systems and the richness of semantics in user queries posed for media search and retrieval. It proposes a unique computational approach to extraction of expressive elements of motion pictures for deriving high-level semantics of stories portrayed, thus enabling rich video annotation and interpretation. This approach, motivated and directed by the existing cinematic conventions known as film grammar, as a first step toward demonstrating its effectiveness, uses the attributes of motion and shot length to define and compute a novel measure of tempo of a movie. Tempo flow plots are defined and derived for a number of full-length movies and edge analysis is performed leading to the extraction of dramatic story sections and events signaled by their unique tempo. The results confirm tempo as a useful high-level semantic construct in its own right and a promising component of others such as rhythm, tone or mood of a film. In addition to the development of this computable tempo measure, a study is conducted as to the usefulness of biasing it toward either of its constituents, namely, motion or shot length. Finally, a refinement is made to the shot length normalizing mechanism, driven by the peculiar characteristics of shot length distribution exhibited by movies. Results of these additional studies, and possible applications and limitations are discussed.

Snapshots of complexity: using motion capture and principal component analysis to reconceptualise dance

This article brings together the disparate worlds of dance practice, motion capture and statistical analysis. Digital technologies such as motion capture offer dance artists new processes for recording and studying dance movement. Statistical analysis of these data can reveal hidden patterns in movement in ways that are semantically ‘blind’, and are hence able to challenge accepted culturo-physical ‘grammars’ of dance creation. The potential benefit to dance artists is to open up new ways of understanding choreographic movement. However, quantitative analysis does not allow for the uncertainty inherent in emergent, artistic practices such as dance. This article uses motion capture and principal component analysis (PCA), a common statistical technique in human movement recognition studies, to examine contemporary dance movement, and explores how this analysis might be interpreted in an artistic context to generate a new way of looking at the nature and role of movement patterning in dance creation.

An adaptive complementary filter for inertial sensor based data fusion to track upper body motion

  Remote human activity monitoring is critical and essential in physiotherapy with respect to the skyrocketing healthcare expenditure and the fast aging population. One of frequently used method to monitor human activity is wearing inertial sensors since it is low-cost and accurate. However, the measurements of those sensors are able only to estimate the orientation and rotation angles with respect to actual movement angles, because of differences in the body’s co-ordination system and the sensor’s co-ordination system. There were numerous studies being conducted to improve the accuracy of estimation, though there is potential for further discussions on improving accuracy by replacing heavy algorithms to less complexity. This research is an attempt to propose an adaptive complementary filter for identifying human upper arm movements. Further, this article discusses a feasibility of upper arm rehabilitation using the proposed adaptive complementary filter and inertial measurement sensors. The proposed algorithm is tested with four healthy subjects wearing an inertial sensor against gold standard, which is the VICON system. It demonstrated root mean squared error of 8.77◦ for upper body limb orientation estimation when compared to gold standard VICON optical motion capture system.

Graphene networks and their influence on free-volume properties of graphene-epoxidized natural rubber composites with a segregated structure: rheological and positron annihilation studies

Epoxidized natural rubber-graphene (ENR-GE) composites with segregated GE networks were successfully fabricated using the latex mixing combined in situ reduced technology. The rheological behavior and electrical conductivity of ENR-GE composites were investigated. At low frequencies, the storage modulus (G′) became frequency-independent suggesting a solid-like rheological behavior and the formation of GE networks. According to the percolation theory, the rheological threshold of ENR-GE composites was calculated to be 0.17 vol%, which was lower than the electrical threshold of 0.23 vol%. Both percolation thresholds depended on the evolution of the GE networks in the composites. At low GE concentrations (<0.17 vol%), GE existed as individual units, while a "polymer-bridged GE network" was constructed in the composites when GE concentrations exceeded 0.17 vol%. Finally, a "three-dimensional GE network" with percolation conductive paths was formed with a GE concentration of 0.23 vol%, where a remarkable increase in the conductivity of ENR-GE composites was observed. The effect of GE on the atom scale free-volume properties of composites was further studied by positron annihilation lifetime spectroscopy and positron age momentum correlation measurements. The motion of ENR chains was retarded by the geometric confinement of "GE networks", producing a high-density interfacial region in the vicinity of GE nanoplatelets, which led to a lower ortho-positronium lifetime intensity and smaller free-volume hole size.

3D motion matching algorithm using signature feature descriptor

This paper introduces a basic frame for rehabilitation motion practice system which detects 3D motion trajectory with the Microsoft Kinect (MSK) sensor system and proposes a cost-effective 3D motion matching algorithm. The rehabilitation motion practice system displays a reference 3D motion in the database system that the player (patient) tries to follow. The player’s motion is traced by the MSK sensor system and then compared with the reference motion to evaluate how well the player follows the reference motion. In this system, 3D motion matching algorithm is a key feature for accurate evaluation for player’s performance. Even though similarity measurement of 3D trajectories is one of the most important tasks in 3D motion analysis, existing methods are still limited. Recent researches focus on the full length 3D trajectory data set. However, it is not true that every point on the trajectory plays the same role and has the same meaning. In this situation, we developed a new cost-effective method that only uses the less number of features called ‘signature’ which is a flexible descriptor computed from the region of ‘elbow points’. Therefore, our proposed method runs faster than other methods which use the full length trajectory information. The similarity of trajectories is measured based on the signature using an alignment method such as dynamic time warping (DTW), continuous dynamic time warping (CDTW) or longest common sub-sequence (LCSS) method. In the experimental studies, we applied the MSK sensor system to detect, trace and match the 3D motion of human body. This application was assumed as a system for guiding a rehabilitation practice which can evaluate how well the motion practice was performed based on comparison of the patient’s practice motion traced by the MSK system with the pre-defined reference motion in a database. In order to evaluate the accuracy of our 3D motion matching algorithm, we compared our method with two other methods using Australian sign word dataset. As a result, our matching algorithm outperforms in matching 3D motion, and it can be exploited for a base framework for various 3D motion-based applications at low cost with high accuracy.

Intra-articular pressure profiles of the cadaveric equine fetlock joint in motion

The study of the influence of motion and initial intra-articular pressure (IAP) on intra-articular pressure profiles in equine cadaver metatarsophalangeal (MTP) joints was undertaken as a prelude to in vivo studies, Eleven equine cadaver MTP joints were submitted to 2 motion frequencies of 5 and 10 cycles/min of flexion and extension, simulating the condition of lower and higher (double) rates of passive motion. These frequencies were applied and pressure profiles generated with initial normal intra-articular pressure (-5 mmHg) and subsequently 30 mmHg intra-articular pressure obtained by injection of previously harvested synovial fluid.The 4 trials performed were 1) normal IAP; 5 cyles/min; 2) normal IAP; 10 cycles/min; 3) IAP at 30 mmHg; 5 cycles/min and 4) IAP at 30 mmHg; 10 cycles/min. The range of joint motion applied (mean +/- s.e.) was 67.6 +/- 1.61 degrees with an excursion from 12.2 +/- 1.2 degrees in extension to 56.2 +/- 2.6 degrees in flexion, Mean pressure recorded in mmHg for the first and last min of each trial, respectively, were 1) -5.7 +/- 0.9 and -6.3 +/- 1.1; 2) -5.3 +/- 1.1 and -6.2 +/- 1.1; 3) 58.8 +/- 8.0 and 42.3 +/- 7.2; 4) 56.6 +/- 3.7 and 40.3 +/- 4.6. Statistical analyses showed a trend for difference between the values for the first and last minute in trial 3 (0.05>P<0.1) with P = 0.1 and significant difference (P = 0.02) between the mean IAP of the first and last min in trial 4. The loss of intra-articular pressure associated with time and motion was 10.5, 16.9, 28.1 and 28.9% for trials 1-4, respectively. As initial intraarticular pressure and motion increased, the percent loss of intra-articular pressure increased.The angle of lowest pressure was 12.2 +/- 1.2 (mean +/- s.e.) in extension in trials 1 and 2, In trials 3 and 4, the lowest pressures were obtained in flexion with the joints at 18.5 +/- 2.0 degrees (mean +/- s.e.). This demonstrated that the joint angle of least pressure changed as the initial intra-articular pressure changed and there would not be a single angle of least pressure for a given joint.The volume of synovial fluid recovered from the MTP joints in trial 3 compared to 4 (trials in which fluid was injected to attain IAP of 30 mmHg) was not significantly different, supporting a soft tissue compliance change as a cause for the significant loss of intra-articular pressure during the 15 min of trial 4.The pressure profiles generated correlate well with in vivo values and demonstrated consistent pressure profiles. Our conclusions are summarised as follows:1. Clinically normal equine MTP joints which were frozen and then later thawed were found to have mostly negative baseline intra-articular pressures, as would be expected in living subjects,2. Alternate pressure profiles of the dorsal and plantar pouch at baseline intra-articular pressure document the presence of pressure forces that would support 'back and forth' fluid movement between joint compartments. This should result in movement of joint fluid during motion, assisting in lubrication and nutrition of articular cartilage,3. If joint pressure was initially greater than normal (30 mmHg), as occurs in diseased equine MTP joints, joint motion further increased joint capsule relaxation (compliance) and, therefore, reduced intra-articular pressure.4. Peak intra-articular pressures reached extremely high values (often >100 mmHg) in flexion when initial pressure was 30 mmHg. Joint effusion pressures recorded for clinical MCP joints are frequently 30 mmHg. These IAP values are expected to produce intermittent synovial ischaemia in clinical cases during joint flexion.5, Additional in vivo studies are necessary to confirm our conclusions from this study and to identify the contributions of fluid absorption and the presence of ischaemia in a vascularised joint.

Solid-state NMR, ionic conductivity, and thermal studies of lithium-doped siloxane-poly(propylene glycol) organic-inorganic nanocomposites

Hybrid organic-inorganic ionic conductors, also called ormolytes (organically modified electrolytes), were obtained by dissolution of LiClO 4 in siloxane-poly(propylene glycol) matrixes. The dynamic features of these nanocomposites were studied and correlated to their electrical properties. Solid-state nuclear magnetic resonance (NMR) spectroscopy was used to probe the effects of the temperature and nanocomposite composition on the dynamic behaviors of both the ionic species ( 7Li) and the polymer chains ( 13C). NMR, dc ionic conductivity, and DSC results demonstrate that the Li + mobility is strongly assisted by the segmental motion of the polymer chain above its glass transition temperature. The ac ionic conductivity in such composites is explained by use of the random free energy barrier (RFEB) model, which is agreement with their disordered and heterogenous structures. These solid ormolytes are transparent and flexible, and they exhibit good ionic conductivity at room temperature (up to 10 -4 S/cm). Consequently, they are very promising candidates for use in several applications such as batteries, sensors, and electrochromic and photoelectro-chemical devices.

Conformational basis for the biological activity of TOAC-labeled angiotensin II and bradykinin: Electron paramagnetic resonance, circular dichroism, and fluorescence studies

N-Terminally and internally labeled analogues of the hormones angiotensin (AII, DRVYIHPF) and bradykinin (BK, RPPGFSPFR) were synthesized containing the paramagnetic amino acid 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4- carboxylic acid (TOAC). TOAC replaced Asp 1 (TOAC 1-AII) and Val 3 (TOAC 3-AII) in AII and was inserted prior to Arg 1 (TOAC 0-BK) and replacing Pro 3 (TOAC 3-BK) in BK. The peptide conformational properties were examined as a function of trifluoroethanol (TFE) content and pH. Electron paramagnetic resonance spectra were sensitive to both variables and showed that internally labeled analogues yielded rotational correlation times (TC) considerably larger than N-terminally labeled ones, evincing the greater freedom of motion of the N-terminus. In TFE, τ C increased due to viscosity effects. Calculation of τ Cpeptide/τ CTOAC ratios indicated that the peptides acquired more folded conformations. Circular dichroism spectra showed that, except for TOAC 1-AII in TFE, the N-terminally labeled analogues displayed a conformational behavior similar to that of the parent peptides. In contrast, under all conditions, the TOAC 3 derivatives acquired more restricted conformations. Fluorescence spectra of All and its derivatives were especially sensitive to the ionization of Tyr 4. Fluorescence quenching by the nitroxide moiety was much more pronounced for TOAC 3-AII The conformational behavior of the TOAC derivatives bears excellent correlation with their biological activity, since, while the N-terminally labeled peptides were partially active, their internally labeled counterparts were inactive [Nakaie, C. R., et al., Peptides 2002, 23, 65-70]. The data demonstrate that insertion of TOAC in the middle of the peptide chain induces conformational restrictions that lead to loss of backbone flexibility, not allowing the peptides to acquire their receptor-bound conformation. © 2004 Wiley Periodicals, Inc.