Subject-coincident coordinate systems and sustained motions

Vestibular research on human perception of self-motion and orientation generally uses the head-based coordinate system standardized by Hixson, Niven, and Correia (1966) for specifying accelerations of the subject. This paper expands the head-based system to include velocities, thereby incorporating both the visual and vestibular systems, and formally defines the resulting concept of asubject-coincident coordinate system. By capturing the organism's vantage point during self-motion, subject-coincident systems give a natural framework for studying the relationship between stimulus, physiology, and perception; however, the essential approach differs from that familiar in traditional physics, so the necessary equations of motion are developed here. In addition, these equations are used to investigate the set ofsustained motions, those motions that can be sustained over a period of time. These motions can cause disorientation and misperception of motion because of saturation or adaptation of the human sensory receptors. The results on sustained motions are summarized in a complete categorization of the set of sustained motions.     

Neighboring general acid participation in thiolester aminolysis in an aprotic solvent

The kinetics of n-butylaminolysis of acyl-substituted phenyl tiolbenzoates in acetonitrile at 25°C was studied. From the second order rate constants a Hammett rho value of 1.45 was obtained. The results indicate a proinounced neighboring group effect in the reaction of phenyl thiolsalicylate, providing the first kinetic evidence for intramolecular general acid participation by a hydroxy function in an aprotic solvent.

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- - 25 °C. , 1,45. -, .

     

Multiple-Edge XAS Studies of Synthetic Iron-Copper Bridged Molecular Assemblies Relevant to Cytochrome c Oxidase. Structure Determination Using Multiple-Scattering Analysis with Statistical Evaluation of Errors

An X-ray absorption spectroscopy study has been carried out at the Fe and Cu K-edges for two bridged molecular assemblies, both of which contain an Fe-X-Cu (X = O(2)(-), OH(-)) bridge unit, some of whose features are relevant to the binuclear site of cytochrome c oxidase. The two complexes [(OEP)Fe-O-Cu(Me(6)tren)](1+) and [(OEP)Fe-(OH)-Cu(Me(5)tren)(OClO(3))](1+) have similar structural fragments around the metal centers except that they differ significantly in the bridge structure (the former contains a linear oxo bridge while the latter has a bent hydroxo bridge). We report a comparative study of these complexes using multiple-scattering (MS) EXAFS analysis and the program package GNXAS. It is found that there is a dramatic increase in the amplitude of the Fe-X-Cu MS pathway as the bridge unit approaches linearity. Full EXAFS MS analysis enables accurate quantitation of bridge metrical details and geometry for both complexes. These studies were done with an expanded version of GNXAS, which allows for simultaneous multiple-edge fitting. Such multiple-edge analysis (using both Fe and Cu edge data) allows common pathways (in this case involving the Fe-X-Cu bridge) to be constrained to be the same, thus improving the observation/variable ratio and enhancing sensitivity for determination of the bridge structure. The accuracy of the structural determination for the bridge units is evaluated by a statistical analysis methodology in which correlations among fitting parameters are identified and contour plots are used to determine random error. The overall error in the EXAFS structural determination is found by establishing the variance with the crystallographically determined values: for the EXAFS-determined parameters at distances below 4 ?, distances and angles deviated on average from crystallographic values by 0.014 ? and 1.5 degrees, respectively. It is also established that structural features in the Fe absorption preedge are diagnostic of oxo vs hydroxo ligation. The relevance of this study to the structural definition of binuclear bridged sites in cytochrome c oxidase and other metalloenzymes is considered.     

A Web-Based, Calculator-Skills Tutorial and Self-Test for General Chemistry Students

We describe the creation and utilization of a collection of Internet-based materials as supplemental instruction for students enrolled in the first-semester course of a general chemistry sequence. These tutorial and self-assessment materials are intended for asynchronous use as a review of mathematical concepts and skills including functional performance with calculators.     

Low field NMR for quality monitoring of 3D printed surimi from cod by-products: Effects of the pH-shift method compared with conventional washing

Implementation of three-dimensional (3D) food printing and novel analytics can reduce food waste and increase utilization of seafood by-products. Low field nuclear magnetic resonance (LF-NMR) and chemometrics were used to investigate the printability and characteristics of surimi pastes from cod by-products as affected by different processing methods (the pH-shift method vs. conventional washing), addition of salt (0, 1.5, and 3%), length of cold storage (0, 4, and 7 days) until 3D printing, and steam cooking. The analysis revealed two to three water populations in the 3D printed samples. Increasing the salt concentration induced myofibrillar swelling in the conventionally prepared surimi, whereas a more salt-induced gelling effect was observed in the pH-shift processed surimi. Cooking had a decreasing effect on the T₂₁ relaxation time and its corresponding apparent population (A₂₁), corresponding to protein denaturation and water loss during cooking. Increasing the salt concentration to 3% had a protective effect towards water exchange between the A₂₁ and A₂₃ populations in the conventionally washed samples but more subtly in the pH-shift samples. Similar trends in relaxation parameters were observed after 4 and 7 days of storage, although the intermediate population A₂₂ seemed to be most affected by the storage. Overall LF-NMR was an effective quality monitoring tool for the physicochemical changes occurring in the 3D printed surimi. The analysis showed both advantages and disadvantages of the two processing methods. However, it can clearly be concluded that increasing the salt content had a stabilizing effect on the surimi, and printing of fresh raw materials is recommended.     

Lineshapes in quasi-elastic scattering from species hopping between non-equivalent surface sites

We present an analytic model applied to quasi-elastic scattering from an adsorbed surface species undergoing jump diffusion between adsorption sites described by a Bravais lattice combined with a basis of multiple points. The model allows for hops between adsorption sites which are both symmetrically and energetically inequivalent. We give results for 1-D hopping, which are applicable to a species jumping between the top and bridge sites along the [11?0] direction on an fcc-(110) surface or for jumps along a step edge. In 2-D, results for hopping between fcc and hcp hollow sites and between the bridge sites of an fcc-(111) surface are presented. These examples give characteristic signatures which will allow these forms of motion to be recognized in experimental data and will enable the underlying physical parameters to be extracted by comparison with the analytical forms derived here.     

Method validation for determination of alkaloid content in goldenseal root powder

A fast, practical ambient extraction methodology followed by isocratic liquid chromatography (LC) analysis with UV detection was validated for the determination of berberine, hydrastine, and canadine in goldenseal (Hydrastis canadensis L.) root powder. The method was also validated for palmatine, a major alkaloid present in the possible bioadulterants Coptis, Oregon grape root, and barberry bark. Alkaloid standard solutions were linear over the evaluated concentration ranges. The analytical method was linear for alkaloid extraction using 0.3-2 g goldenseal root powder/100 mL extraction solvent. Precision of the method was demonstrated using 10 replicate extractions of 0.5 g goldenseal root powder, with percent relative standard deviation for all 4 alkaloids < or = 1.6. Alkaloid recovery was determined by spiking each alkaloid into triplicate aliquots of neat goldenseal root powder. Recoveries ranged from 92.3% for palmatine to 101.9% for hydrastine. Ruggedness of the method was evaluated by performing multiple analyses of goldenseal root powder from 3 suppliers over a 2-year period. The method was also used to analyze Coptis root, Oregon grape root, barberry bark, and celandine herb, which are possible goldenseal bioadulterants. The resulting chromatographic profiles of the bioadulterants were significantly different from that of goldenseal. The method was directly transferred to LC with mass spectrometry, which was used to confirm the presence of goldenseal alkaloids tetrahydroberberastine, berberastine, canadaline, berberine, hydrastine, and canadine, as well as alkaloids from the bioadulterants, including palmatine, jatrorrhizine, and coptisine.     

Theta Series of Quaternion Algebras over Function Fields

Let K be the function field over a finite field of odd order, and let H be a definite quaternion algebra over K. If Λ is an order of level M in H, we define theta series for each ideal I of Λ using the reduced norm on H. Using harmonic analysis on the completed algebra H_∞ and the arithmetic of quaternion algebras, we establish a transformation law for these theta series. We also define analogs of the classical Hecke operators and show that in general, the Hecke operators map the theta series to a linear combination of theta series attached to different ideals, a generalization of the classical Eichler Commutation Relation.