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Method to Determine the Distribution of Substituted or Intercalated Ions in Transition-Metal Dichalcogenides: Fe x VSe 2 and Fe 1– x V x Se 2

Multiple techniques are combined to determine the amount of intercalation and/or substitution in transition-metal dichalcogenides. Kiessig fringes in the X-ray reflectivity pattern are used to calculate thickness. Laue oscillations in the specular diffraction pattern of the crystallographically aligned samples determine the number of unit cells in the coherently diffracting domains. The amount of impurity phase(s) is estimated by the difference between the thickness of the films and the size of the domains. If the difference is small relative to the total film thickness, the composition of the crystalline phase can be determined from X-ray fluorescence measurements. The number of unit cells possible can be calculated from the amount of each element determined by X-ray fluorescence measurements using in-plane lattice parameters, and the amount of the anion should agree with the number of unit cells determined from the Laue oscillations. The total amount of the metal relative to that required for the number of unit cells from the Laue oscillations provides a direct determination of the relative amount of intercalation and/or substitution in the crystalline dichalcogenide. So the utility of this approach is illustrated in Fe x V 1–y Se 2 samples. The relative amount of intercalation versus substitution was determined independently using electron microscopy and Rietveld refinement of diffraction patterns and is consistent with this new approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determination of the onset time in polarization power ratio Z/H for precursor of Sumatra earthquake

Determination of onset time precursors of strong earthquakes (Mw > 5) and distance (d < 500 km) using geomagnetic data from Geomagnetic station KTB, Sumatra and two station references DAV, Philippine and DAW, Australia. separate techniques are required in its determination. Not the same as that recorded in the kinetic wave seismograms can be determined by direct time domain. Difficulties associated with electromagnetic waves seismogenic activities require analysis of the transformed signal in the frequency domain. Determination of the frequency spectrum will determine the frequency of emissions emitted from the earthquake source. The aim is to analyze the power amplitude of the ULF emissions in the horizontal component (H) and vertical component (Z). Polarization power ratio Z/H is used for determining the sign of earthquake precursors controlled by the standard deviation. The pattern recognition polarization ratio should be obtained which can differentiate emissions from seismogenic effects of geomagnetic activity. ULF emission patterns generated that seismogenic effect has duration > 5 days and the dominance of emission intensity recorded at the Z component and for the dominance of the emission intensity of geomagnetic activity recorded in the component H. The result shows that the onset time is determined when the polarization power ratio Z/H standard deviation over the limit (p ± 2 σ) which has a duration of > 5 days.

58 GEOSCIENCES↗

A feasibility and optimization study to determine cooling time and burnup of advanced test reactor fuels using a nondestructive technique

The goal of this study presented is to determine the best available non-destructive technique necessary to collect validation data as well as to determine burn-up and cooling time of the fuel elements onsite at the Advanced Test Reactor (ATR) canal. This study makes a recommendation of the viability of implementing a permanent fuel scanning system at the ATR canal and leads3 to the full design of a permanent fuel scan system. The study consisted at first in determining if it was possible and which equipment was necessary to collect useful spectra from ATR fuel elements at the canal adjacent to the reactor. Once it was establish that useful spectra can be obtained at the ATR canal the next step was to determine which detector and which configuration was better suited to predict burnup and cooling time of fuel elements non-destructively. Three different detectors of High Purity Germanium (HPGe), Lanthanum Bromide (LaBr3), and High Pressure Xenon (HPXe) in two system configurations of above and below the water pool were used during the study. The data collected and analyzed was used to create burnup and cooling time calibration prediction curves for ATR fuel. The next stage of the study was to determine which of the three detectors tested was better suited for the permanent system. From spectra taken and the calibration curves obtained, it was determined that although the HPGe detector yielded better results, a detector that could better withstand the harsh environment of the ATR canal was needed. The in-situ nature of the measurements required a rugged fuel scanning system, low in maintenance and easy to control system. Based on the ATR canal feasibility measurements and calibration results it was determined that the LaBr3 detector was the best alternative for canal in-situ measurements; however in order to enhance the quality of the spectra collected using this scintillator a deconvolution method was developed. Following the development of the deconvolution method for ATR applications the technique was tested using one-isotope, multi-isotope and fuel simulated sources. Burnup calibrations were perfomed using convoluted and deconvoluted data. The calibrations results showed burnup prediction by this method improves using deconvolution. The final stage of the deconvolution method development was to perform an irradiation experiment in order to create a surrogate fuel source to test the deconvolution method using experimental data. A conceptual design of the fuel scan system is path forward using the rugged LaBr3 detector in an above the water configuration and deconvolution algorithms.

07 ISOTOPE AND RADIATION SOURCES↗

Ionospheric refraction effects on TOPEX orbit determination accuracy using the Tracking and Data Relay Satellite System (TDRSS)

This investigation concerns the effects on Ocean Topography Experiment (TOPEX) spacecraft operational orbit determination of ionospheric refraction error affecting tracking measurements from the Tracking and Data Relay Satellite System (TDRSS). Although tracking error from this source is mitigated by the high frequencies (K-band) used for the space-to-ground links and by the high altitudes for the space-to-space links, these effects are of concern for the relatively high-altitude (1334 kilometers) TOPEX mission. This concern is due to the accuracy required for operational orbit-determination by the Goddard Space Flight Center (GSFC) and to the expectation that solar activity will still be relatively high at TOPEX launch in mid-1992. The ionospheric refraction error on S-band space-to-space links was calculated by a prototype observation-correction algorithm using the Bent model of ionosphere electron densities implemented in the context of the Goddard Trajectory Determination System (GTDS). Orbit determination error was evaluated by comparing parallel TOPEX orbit solutions, applying and omitting the correction, using the same simulated TDRSS tracking observations. The tracking scenarios simulated those planned for the observation phase of the TOPEX mission, with a preponderance of one-way return-link Doppler measurements. The results of the analysis showed most TOPEX operational accuracy requirements to be little affected by space-to-space ionospheric error. The determination of along-track velocity changes after ground-track adjustment maneuvers, however, is significantly affected when compared with the stringent 0.1-millimeter-per-second accuracy requirements, assuming uncoupled premaneuver and postmaneuver orbit determination. Space-to-space ionospheric refraction on the 24-hour postmaneuver arc alone causes 0.2 millimeter-per-second errors in along-track delta-v determination using uncoupled solutions. Coupling the premaneuver and postmaneuver solutions, however, appears likely to reduce this figure substantially. Plans and recommendations for response to these findings are presented.

Radomski, M. S.↗

Improved solution accuracy for TDRSS-based TOPEX/Poseidon orbit determination

Orbit determination results are obtained by the Goddard Space Flight Center (GSFC) Flight Dynamics Division (FDD) using a batch-least-squares estimator available in the Goddard Trajectory Determination System (GTDS) and an extended Kalman filter estimation system to process Tracking and Data Relay Satellite (TDRS) System (TDRSS) measurements. GTDS is the operational orbit determination system used by the FDD in support of the Ocean Topography Experiment (TOPEX)/Poseidon spacecraft navigation and health and safety operations. The extended Kalman filter was implemented in an orbit determination analysis prototype system, closely related to the Real-Time Orbit Determination System/Enhanced (RTOD/E) system. In addition, the Precision Orbit Determination (POD) team within the GSFC Space Geodesy Branch generated an independent set of high-accuracy trajectories to support the TOPEX/Poseidon scientific data. These latter solutions use the geodynamics (GEODYN) orbit determination system with laser ranging and Doppler Orbitography and Radiopositioning integrated by satellite (DORIS) tracking measurements. The TOPEX/Poseidon trajectories were estimated for November 7 through November 11, 1992, the timeframe under study. Independent assessments were made of the consistencies of solutions produced by the batch and sequential methods. The batch-least-squares solutions were assessed based on the solution residuals, while the sequential solutions were assessed based on primarily the estimated covariances. The batch-least-squares and sequential orbit solutions were compared with the definitive POD orbit solutions. The solution differences were generally less than 2 meters for the batch-least-squares and less than 13 meters for the sequential estimation solutions. After the sequential estimation solutions were processed with a smoother algorithm, position differences with POD orbit solutions of less than 7 meters were obtained. The differences among the POD, GTDS, and filter/smoother solutions can be traced to differences in modeling and tracking data types, which are being analyzed in detail.

Doll, C. E.↗

Determination of Residual Stress in Composite Materials Using Ultrasonic Waves

The performance of high temperature composites can be significantly affected by the presence of residual stresses. These stresses arise during cooling processes from fabrication to room temperature due to mismatch of thermal expansion coefficients between matrix and fiber materials. This effect is especially pronounced in metal matrix and intermetallic composites. It can lead to plastic deformations, matrix cracking and fiber/matrix interface debonding. In this work the feasibility of ultrasonic techniques for residual stress assessment in composites is addressed. A novel technique for absolute stress determination in orthotropic materials from angular dependencies of ultrasonic velocities is described. The technique is applicable for determination of both applied and residual stresses and does not require calibration measurements on a reference sample. The important advantage of this method is that stress is determined simultaneously with stress-dependent elastic constants and is thus decoupled from the material texture. It is demonstrated that when the principal plane stress directions coincide with acoustical axes, the angular velocity data in the plane perpendicular to the stress plane may be used to determine both stress components. When the stress is off the acoustical axes, the shear and the difference of the normal stress components may be determined from the angular dependence of group velocities in the plane of stresses. Synthetic sets of experimental data corresponding to materials with different anisotropy and stress levels are used to check the applicability of the technique. The method is also verified experimentally. A high precision ultrasonic wave transmission technique is developed to measure angular dependence of ultrasonic velocities. Examples of stress determination from experimental velocity data are given. A method is presented for determination of velocities of ultrasonic waves propagating through the composite material with residual stresses. It is based on the generalized self-consistent multiple scattering model. Calculation results for longitudinal and shear ultrasonic wave velocities propagating perpendicular to the fibers direction in SCS-6/Ti composite with and without residual stresses are presented. They show that velocity changes due to presence of stresses are of order 1%.

Rokhlin, S. I.↗

Semi-Major Axis Knowledge and GPS Orbit Determination

In recent years spacecraft designers have increasingly sought to use onboard Global Positioning System receivers for orbit determination. The superb positioning accuracy of GPS has tended to focus more attention on the system's capability to determine the spacecraft's location at a particular epoch than on accurate orbit determination, per se. The determination of orbit plane orientation and orbit shape to acceptable levels is less challenging than the determination of orbital period or semi-major axis. It is necessary to address semi-major axis mission requirements and the GPS receiver capability for orbital maneuver targeting and other operations that require trajectory prediction. Failure to determine semi-major axis accurately can result in a solution that may not be usable for targeting the execution of orbit adjustment and rendezvous maneuvers. Simple formulas, charts, and rules of thumb relating position, velocity, and semi-major axis are useful in design and analysis of GPS receivers for near circular orbit operations, including rendezvous and formation flying missions. Space Shuttle flights of a number of different GPS receivers, including a mix of unfiltered and filtered solution data and Standard and Precise Positioning Service modes, have been accomplished. These results indicate that semi-major axis is often not determined very accurately, due to a poor velocity solution and a lack of proper filtering to provide good radial and speed error correlation.

Carpenter, J. Russell↗

Semi-Major Axis Knowledge and GPS Orbit Determination

In recent years spacecraft designers have increasingly sought to use onboard Global Positioning System receivers for orbit determination. The superb positioning accuracy of GPS has tended to focus more attention on the system's capability to determine the spacecraft's location at a particular epoch than on accurate orbit determination, per se. The determination of orbit plane orientation and orbit shape to acceptable levels is less challenging than the determination of orbital period or semi-major axis. It is necessary to address semi-major axis mission requirements and the GPS receiver capability for orbital maneuver targeting and other operations that require trajectory prediction. Failure to determine semi-major axis accurately can result in a solution that may not be usable for targeting the execution of orbit adjustment and rendezvous maneuvers. Simple formulas, charts, and rules of thumb relating position, velocity, and semi-major axis are useful in design and analysis of GPS receivers for near circular orbit operations, including rendezvous and formation flying missions. Space Shuttle flights of a number of different GPS receivers, including a mix of unfiltered and filtered solution data and Standard and Precise Positioning, Service modes, have been accomplished. These results indicate that semi-major axis is often not determined very accurately, due to a poor velocity solution and a lack of proper filtering to provide good radial and speed error correlation.

Carpenter, J. Russell↗

A Study into the Method of Precise Orbit Determination of a HEO Orbiter by GPS and Accelerometer

In the present day, orbit determination by Global Positioning System (GPS) is not unusual. Especially for low-cost small satellites, position determination by an on-board GPS receiver provides a cheap, reliable and precise method. However, the original purpose of GPS is for ground users, so the transmissions from all of the GPS satellites are directed toward the Earth s surface. Hence there are some restrictions for users above the GPS constellation to detect those signals. On the other hand, a desire for precise orbit determination for users in orbits higher than GPS constellation exists. For example, the next Japanese Very Long Baseline Interferometry (VLBI) mission "ASTRO-G" is trying to determine its orbit in an accuracy of a few centimeters at apogee. The use of GPS is essential for such ultra accurate orbit determination. This study aims to construct a method for precise orbit determination for such high orbit users, especially in High Elliptical Orbits (HEOs). There are several approaches for this objective. In this study, a hybrid method with GPS and an accelerometer is chosen. Basically, while the position cannot be determined by an on-board GPS receiver or other Range and Range Rate (RARR) method, all we can do to estimate the user satellite s position is to propagate the orbit along with the force model, which is not perfectly correct. However if it has an accelerometer (ACC), the coefficients of the air drag and the solar radiation pressure applied to the user satellite can be updated and then the propagation along with the "updated" force model can improve the fitting accuracy of the user satellite s orbit. In this study, it is assumed to use an accelerometer available in the present market. The effects by a bias error of an accelerometer will also be discussed in this paper.

Ikenaga, Toshinori↗

Development of online pulse-finding algorithms for the Mu2e Stopping Target Monitor and an evaluation of the signal to background ratio for the Mu2e stopped-muon rate determination

This thesis presents a determination of the acceptance of the Mu2e Stopping Target Monitor (STM) detector for both signal and background events. The rate of X-rays of a specific energy in the STM is used to determine the rate of stopped muons in the aluminium stopping target, which is used as the normalisation for all Mu2e measurements, particularly the branching ratio for a charged lepton flavour violating (cLFV) process. The acceptance for the 347\,keV $2p-1s$ aluminium signal X-ray is determined to be $(8.03 \pm 0.05) \times 10^{-10}$\,cm$^{-2}$ and the acceptance for the background photons (at 347\,keV) to be $(3.19 \pm 0.21) \times 10^{-8}$\,cm$^{-2}$. This results in a signal-to-background ratio of approximately two which is significantly higher than had previously been estimated. These signal-to-background rates are used to determine the time required to achieve a statistical uncertainty of 10\% on the number of 347\,keV X-rays as a function of the detector resolution and back ground rate. For a resolution of 2\,keV, and the background rate determined in this thesis, approximately one minute of data is required. The three corrections needed to be applied to the measured 347\,keV rate to determine the rate of stopped muons are also determined and potential sources of bias arising from the background shape, background fit range and energy calibration are investigated and found to be insignificant. The raw energy of the particles in the STM detector comes from a 16-bit ADC digitising at $\sim 300$\,MHz. It is not possible to store all the raw digitisations and online algorithms have been developed to rapidly select pulses in the detector and reconstruct their energy. The performance of these algorithms has been characterised with simulated data as a function of detector rate and resolution and optimum operating points for the algorithms have been defined. The integrity of the algorithms has also been demonstrated and characterised on test-beam data at high r ates and with radioactive sources at low rates.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Spacecraft Modeling, Attitude Determination, and Control: Quaternion-Based Approach

Spacecraft attitude determination and control is an important part of a spacecraft to achieve its designed mission. As of today, many spacecrafts have been successfully launched, and most of them have performed well as they were designed. Many research papers have been published to address the attitude determination and control design problems. Several text books are available for students to learn the technology and for engineers to use as references. The most popular spacecraft models for attitude determination algorithms and control design methods are the Euler angle models and the quaternion models . The Euler angle models have been proved very efficient as the linearized models are controllable, and all standard linear control system design methods are directly applicable. The drawbacks related to the Euler angle methods are (a) the designs based on linearized models may not globally stabilize the original nonlinear spacecraft, i.e., the design may not work when the attitude of the spacecraft is far away from the point where the linearization is performed; (b) the models depend on the rotational sequences, this can be error prone if several teams work on the same project and they use different rotational sequences; (c) for any rotational sequence, there is a singular point where the model is not applicable; and (d) since most attitude determination methods use quaternion to represent the spacecraft attitude, there is a need to transform quaternion into Euler angles. On the other hand, for quaternion models, people have found controllers that can globally stabilize nonlinear spacecraft systems; the models do not depend on rotational sequences and they have no singular point; and the quaternion is provided by attitude determination system and ready to use. The main problem with the quaternion model based control system design is that the linearized quaternion model is not controllable. Therefore, most published design methods heavily rely on Lyapunov functions for the nonlinear spacecraft system. But there is no systematic way to obtain a desired Lyapunov functions. Moreover, the Lyapunov function based designs focus on the closed-loop system stability but pay little attention to the closed-loop system performance. In a series of papers, the author proposed some reduced quaternion models which lead to some controllable linearized spacecraft models. Therefore, all standard linear system theory can be directly applied to analyze and design the spacecraft control systems. We showed that, in some cases, the designed control system is not only optimal for the linearized system, but also globally stabilize the original nonlinear system . Clearly, the reduced quaternion models do not depend on rotational sequences. Due to the special structure of the linearized spacecraft model, some most important design methods, such as LQR design and robust pole assignment design are very simple, enjoy the analytical solutions for some problems, have direct connection to the performance measures, such as settling time, rising time , and percentage of overshoot . All these features are attractive for high quality control system designs. The idea mentioned above is then extended to more spacecraft control problems using specific actuators such as magnetic torque bars and control momentum gyroscopes. These types of actuators may not provide exactly desired torques. Most existing methods use different conversions to get approximate solutions, meaning that these actuators may generate a torque close to but not equal to the desired one. Using the reduced quaternion models that incorporate the actuators into the system model, the control inputs are not torques but the operational parameters. The main benefit of this idea is that the control actions are not approximate but accurate. As all actuators have their operational limit, design with input constraints are also considered in this book by using recently developed interior-point optimization techniques. This book grows up from my research on the spacecraft attitude determination and control design methods in more than a decade which is focused on using reduced quaternion models because of their merits stated above. The book provides all necessary background materials on orbital dynamics, rotations and quaternion, frequently used reference frames, transformations between reference frames, space environment and disturbance torques, ephemeris astronomical vector calculations and measurement instruments, spacecraft control actuators and their models, so that the readers will get a global picture and can apply all these information into the spacecraft system modeling, attitude determination, and spacecraft control system designs, which is the main purpose of this book. This book is different from existing books in that we focus on quaternion based spacecraft control system designs and we consider only attitude control system design related problems, from spacecraft modeling, to attitude determination and estimation, to control system design method selection, to control algorithm development, and to the simulation of the control system designs. Moreover, this book addresses different attitude control tasks in the spacecraft life cycle, including spacecraft maneuver, orbit raising, attitude control, and rendezvous. Finally, this book emphasizes the state space design methods rather than the classical frequency design methods.

Attitude determination and control↗

Using Project Complexity Determinations to Establish Required Levels of Project Rigor

The concepts discussed in this paper 1) focus on using technical competencies and skills in making objective determinations regarding project complexity based on objective scoring criteria and 2) then using the complexity determinations to establish the level of rigor required in initiating, planning, executing, monitoring and controlling, and closing projects to maximize process efficiency. This paper presents a project complexity analysis methodology for defining the levels of project management process rigor a project team needs to employ to maximize project delivery efficiencies without compromising quality and performance. Methods for making project complexity determinations based on project lifecycle size, duration, organizational complexity, requirements, technology readiness, risk, and visibility are discussed. The paper correlates the levels of rigor needed by project management process groups given the determined level of project complexity. Next, the paper presents a graded approach to defining extent of team formation, planning documentation rigor, stakeholder communication rigor, requirements management rigor, acquisition planning, risk management, executing, and monitoring and controlling rigor dependent on project complexity determinations. Methods for integrating and aligning the project complexity determination methods into existing project management procedures and processes are also discussed as well as methods for training personnel in the use of the method and facilitating and monitoring effectiveness of implementation within an organization in which project delivery is a mission focus.

complexity, project, determination, management, tr↗

Characterization of a large sex determination region in Salix purpurea L. (Salicaceae)

Dioecy has evolved numerous times in plants, but heteromorphic sex chromosomes are apparently rare. Sex determination has been studied in multiple Salix and Populus (Salicaceae) species, and P. trichocarpa has an XY sex determination system on chromosome 19, while S. suchowensis and S. viminalis have a ZW system on chromosome 15. Here in this paper, we use whole genome sequencing coupled with quantitative trait locus mapping and a genome-wide association study to characterize the genomic composition of the non-recombining portion of the sex determination region. We demonstrate that Salix purpurea also has a ZW system on chromosome 15. The sex determination region has reduced recombination, high structural polymorphism, an abundance of transposable elements, and contains genes that are involved in sex expression in other plants. We also show that chromosome 19 contains sex-associated markers in this S. purpurea assembly, along with other autosomes. This raises the intriguing possibility of a translocation of the sex determination region within the Salicaceae lineage, suggesting a common evolutionary origin of the Populus and Salix sex determination loci.

59 BASIC BIOLOGICAL SCIENCES↗

Efficiency Improvement in a Busy Radiology Practice: Determination of Musculoskeletal Magnetic Resonance Imaging Protocol Using Deep-Learning Convolutional Neural Networks

The purposes of this study are to evaluate the feasibility of protocol determination with a convolutional neural networks (CNN) classifier based on short-text classification and to evaluate the agreements by comparing protocols determined by CNN with those determined by musculoskeletal radiologists. Following institutional review board approval, the database of a hospital information system (HIS) was queried for lists of MRI examinations, referring department, patient age, and patient gender. These were exported to a local workstation for analyses: 5258 and 1018 consecutive musculoskeletal MRI examinations were used for the training and test datasets, respectively. The subjects for pre-processing were routine or tumor protocols and the contents were word combinations of the referring department, region, contrast media (or not), gender, and age. The CNN Embedded vector classifier was used with Word2Vec Google news vectors. The test set was tested with each classification model and results were output as routine or tumor protocols. The CNN determinations were evaluated using the receiver operating characteristic (ROC) curves. The accuracies were evaluated by a radiologist-confirmed protocol as the reference protocols. The optimal cut-off values for protocol determination between routine protocols and tumor protocols was 0.5067 with a sensitivity of 92.10%, a specificity of 95.76%, and an area under curve (AUC) of 0.977. The overall accuracy was 94.2% for the ConvNet model. All MRI protocols were correct in the pelvic bone, upper arm, wrist, and lower leg MRIs. Deep-learning-based convolutional neural networks were clinically utilized to determine musculoskeletal MRI protocols. CNN-based text learning and applications could be extended to other radiologic tasks besides image interpretations, improving the work performance of the radiologist.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Spectrophotometric Determination of Tris(2-Chloroethyl)Amine Using Acid Dyes

Methods of extraction-spectrophotometric determination of tris(2-chloroethyl)amine using nine acid dyes from the groups of sulfonephthaleins, sulfonated anthraquinones, and azo dyes have been developed. These procedures are based on the formation of the ion associates of the reactants and their extraction into chloroform. The conditions of the determination were optimized to determine the optimal pH for extraction from the water phase, the optimal excess of the dye, and the time needed for the extraction. The limits of detection and determination, the molar absorptivities of ion associates, extraction efficiency, distribution ratio, and conditional extraction constants for the separate procedures of determination were calculated. Of the studied acid dyes, the most suitable agents for determining the analyte were bromothymol blue and Acid Blue 129. These procedures are relatively undemanding in terms of time and instruments required and can be applied in field analysis of nitrogen mustards.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

General Method for Determining Redox Potentials without Electrolyte

A novel method to determine redox potentials without electrolyte is presented here. The method is based on a new ability to determine the dissociation constant, $K°_d$, for ion pairs formed between any radical anion and any inert electrolyte counterion. These dissociation constants can be used to determine relative shifts of redox potential as a function of electrolyte concentration, connecting referenced potentials determined with electrochemistry (with 0.1 M electrolyte) to electrolyte-free values. Pulse radiolysis created radical anions enabling determination of equilibrium constants for electron transfer between anions of donor and acceptor molecules as a function of electrolyte concentration in THF. The measurements determined “composite equilibrium constants”, $K_{eqC}$, which contain information about the dissociation constant for the electrolyte cations, X + , with the radical anions of both the donor, $K°_d$(D –• ,X + ) and the acceptor, $K°_d$(A –• ,X + ). Dissociation constants were obtained for a selection of radical anions with tetrabutylammonium (TBA + ). The electrolyte was found to shift the reduction potentials of small molecules 1-methylpyrene and trans-stilbene by close to +130 mV whereas oligo-fluorenes and polyfluorenes experienced shifts of only (+25 ± 6) mV due to charge delocalization weakening the ion pair. These shifts for reduction of aromatic hydrocarbon molecules are smaller than shifts of +232 and +451 mV seen previously for benzophenone radical anion with TBA + and Na + respectively where the charge on the radical anion is localized largely on one C=O bond, thus forming a more tightly bound ion pair.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single locus sex determination and female heterogamety in the basket willow ( Salix viminalis L.)

Most eukaryotes reproduce sexually and a wealth of different sex determination mechanisms have evolved in this lineage. Dioecy or separate sexes are rare among flowering plants but have repeatedly evolved from hermaphroditic ancestors possibly involving male or female sterility mutations. Willows (Salix spp.) and poplars (Populus spp.) are predominantly dioecious and are members of the Salicaceae family. All studied poplars have sex determination loci on chromosome XIX, however, the position differs among species and both male and female heterogametic system exists. In contrast to the situation in poplars, knowledge of sex determination mechanisms in willows is sparse. In the present study, we have for the first time positioned the sex determination locus on chromosome XV in S. viminalis using quantitative trait locus mapping. All female offspring carried a maternally inherited haplotype, suggesting a system of female heterogamety or ZW. We used a comparative mapping approach and compared the positions of the markers between the S. viminalis linkage map and the physical maps of S. purpurea, S. suchowensis and P. trichocarpa. As we found no evidence for chromosomal rearrangements between chromosome XV and XIX between S. viminalis and P. trichocarpa, it shows that the sex determination loci in the willow and the poplar most likely do not share a common origin and has thus evolved separately. This demonstrates that sex determination mechanisms in the Salicaceae family have a high turnover rate and as such it is excellent for studies of evolutionary processes involved in sex chromosome turnover.

59 BASIC BIOLOGICAL SCIENCES↗

Direct analysis of cotton swipes for plutonium isotope determination by microextraction-ICP-MS

This study demonstrates a method for determining the isotopic composition of low-level (sub-pg) plutonium (Pu) directly from a cotton swipe. Environmental sample (ES) swipes are routinely employed as a tool for monitoring activities in nuclear facilities. Traditional ES swipe analysis, as employed in nuclear safeguards, utilizes laborious ashing, digestion, and chemical separation procedures prior to mass spectrometric (MS) analysis. Here, an innovative sample introduction technique employing a microextraction probe to extract Pu directly from the swipe surface is described. The microextraction probe lowers onto the swipe surface, seals on a small area (8 mm 2 ), and delivers solvent (2% HNO 3 ) to extract actinide material that may be present. The extracted analyte is subsequently directed into a sector field inductively coupled plasma (ICP)-MS for isotope ratio determination. This microextraction-ICP-MS method successfully determined the isotopic composition ( 240 Pu/ 239 Pu and 242 Pu/ 239 Pu) of three Pu certified reference materials (CRM 136, 137, and 138) that were deposited (1 pg) onto ES swipes. The percent relative difference from the certified value, uncorrected for instrumental fractionation, was <2% for the 240 Pu/ 239 Pu ratio on all three CRMs and <10% for the 242 Pu/ 239 Pu ratio on CRM 136 and 138. Here, the percent relative standard deviation, an estimate of the sample-to-sample isotopic precision, was <4% for the 240 Pu/ 239 Pu and <15% for the 242 Pu/ 239 Pu. Method limits of detection were determined, based on measurements of an enriched 244 Pu material, to be ~7 fg. Additionally, a mixed uranium (U) and Pu deposition was made to determine the method's ability to simultaneously extract U and Pu and determine the isotopic composition of both analytes.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗