Direct, uncorrected, molecule-free analysis of 236U from uranium-bearing particles with NAUTILUS: a new kind of mass spectrometer.

We demonstrate use of the Naval Ultra-Trace Isotope Laboratory's Universal Spectrometer (NAUTILUS) at the U.S. Naval Research Laboratory (NRL) to measure 236U directly from uranium-bearing particles free from molecular isobaric interferences. Particles with 235U enrichments in the range of 0.32% to 3.28% and 236U enrichments from no enrichment to 0.015% provided by the International Atomic Energy Agency (IAEA) were analyzed directly using the NAUTILUS. We report the experimental data here without correcting for molecular hydrides and/or applying any other background subtractions. The results from all samples agreed with the certified values within standard error save for the 236U composition of the IRMM 023, which suffered from a combination of insufficient particle sizes and sub-µmol mol-1 236U concentrations. We were able, however, to directly measure as low as three µmol mol-1 of 236U in individual particles regardless of the 235U concentration. Our results are comparable with Large Geometry Secondary Ion Mass Spectrometry (LG-SIMS) and serve as baseline for a more comprehensive comparison between LG-SIMS and the NAUTILUS in the future. Moreover, we demonstrate the ability of the NAUTILUS to generate raster ion images with the same ease as traditional LG-SIMS instruments. By combining our ability to measure 236U directly with raster ion imaging, we were able to detect a low intensity, small uranium-bearing particle in the presence of high molecular backgrounds for a non-ideal sample. This discovery could lead to more targeted and, therefore, less time intensive particle screening methodologies.

Secondary ion mass spectrometry signatures for verifying declarations of fissile-material production.

Direct analysis of uranium enrichment facility components were performed using secondary ion mass spectrometry (SIMS). A standard protocol was developed to enable preparation of SIMS samples from a corroded pipe piece without disturbing the corrosion layer. Unique uranium, oxygen and fluorine containing signatures were discovered in the corrosion layer by performing a mass scan of the region of interest from 230 to 280amu. These signatures identified the source of the corrosion layer as uranium hexafluoride (UF6) or an associated hydrolysis product. Isotopic analysis of the corrosion layer determined enrichment of (235)U to a value of 0.0116±0.0019 for the (235)U/(238)U isotopic ratio as compared to the NIST traceable standard (CRM 112-A) with a natural (235)U/(238)U isotopic ratio of 0.007254±0.000004. SIMS depth analysis revealed that the corrosion layer was isotopically homogenous to a depth of ~23.5µm. Optical profilometry measurements prior to and following SIMS depth analysis were used to determine a sputter rate of 0.48nm/s for 18.5keV O(-) ion bombardment of the corrosion layer. The data presented is conclusive evidence that SIMS depth analysis can be used to identify novel nuclear archeology signatures from uranium enrichment components and perform meaningful isotopic analysis of these signatures.

Avoiding stay in the intensive care unit after liver transplantation: a score to assign location of care.

Select liver transplantation (LT) recipients in our program are transferred from operating room to postanesthesia care unit for recovery and extubation with transfer to the ward, completely eliminating an intensive care unit (ICU) stay. Developing a reliable method to determine patients suitable for fast-tracking would be of practical benefit to centers considering this practice. The aim of this study was to create a fast-tracking probability score that could be used to predict successful assignment of care location after LT. Recipient, donor and operative characteristics were assessed for independent association with successful fast-tracking to create a probability score. Of the 1296 LT recipients who met inclusion criteria, 704 (54.3%) were successfully fast-tracked and 592 (45.7%) were directly admitted to the ICU after LT. Based on nine readily available variables at the time of LT, we created a scoring system that classified patients according to the likelihood of being successfully fast-tracked to the surgical ward, with an area under the curve (AUC) of 0.790 (95% CI: 0.765-0.816). This score was validated in an independent group of 372 LT with similar AUC. We describe a score that can be used to predict successful fast-tracking immediately after LT using readily available clinical variables.

Association of surgeon with surgical site infection after liver transplantation.

Surgical site infection (SSI) after liver transplantation has been associated with increased risk of allograft loss and death. Identification of modifiable risk factors for these infections is imperative. To our knowledge, intraoperative practices associated with transplant surgeons have not been assessed as a risk factor. A retrospective cohort study of risk factors for SSI after 1036 first liver transplantations completed by seven surgeons at a single center between 2003 and 2008 was undertaken. Cox proportional hazards models were used to evaluate the association between surgeons and SSIs. SSIs were identified in 166 of 1036 patients (16%). Single variable analysis showed strong evidence of an association between surgeon and SSI (p = 0.0007); the estimated cumulative incidence of SSI ranged from 7% to 24%. This result was consistent in multivariable analysis adjusting for potentially confounding variables (p = 0.002). The occurrence of organ-space or deep SSI varied significantly among surgeons in both single variable analysis (p = 0.005) and multivariable analysis (p = 0.006). These findings provide evidence that differences in the surgical practices of individual surgeons are associated with risk for SSI after liver transplantation. Identification of specific surgical practices associated with risk of SSI is warranted.

Investigating the Fundamentals of Molecular Depth Profiling Using Strong-field Photoionization of Sputtered Neutrals.

Molecular depth profiles of model organic thin films were performed using a 40 keV C60+ cluster ion source in concert with TOF-SIMS. Strong-field photoionization of intact neutral molecules sputtered by 40 keV C60+ primary ions was used to analyze changes in the chemical environment of the guanine thin films as a function of ion fluence. Direct comparison of the secondary ion and neutral components of the molecular depth profiles yields valuable information about chemical damage accumulation as well as changes in the molecular ionization probability. An analytical protocol based on the erosion dynamics model is developed and evaluated using guanine and trehalose molecular secondary ion signals with and without comparable laser photoionization data.

Temperature effects in the sputtering of a molecular solid by energetic atomic and cluster projectiles.

Temperature effects in the sputtering of an organic molecule were investigated by subjecting a well defined film of coronene to Au1 and C60 primary ions at 100 and 300 K. Strong field photoionization of the sputtered neutral flux was employed to monitor the change in flight time and kinetic energy distributions of intact and fragmented species.

Strong-field Photoionization of Sputtered Neutral Molecules for Molecular Depth Profiling.

Molecular depth profiles of an organic thin film of guanine vapor deposited onto a Ag substrate are obtained using a 40 keV C(60) cluster ion beam in conjunction with time-of-flight secondary ion mass spectrometric (ToF-SIMS) detection. Strong-field, femtosecond photoionization of intact guanine molecules is used to probe the neutral component of the profile for direct comparison with the secondary ion component. The ability to simultaneously acquire secondary ions and photoionized neutral molecules reveals new fundamental information about the factors that influence the properties of the depth profile. Results show that there is an increased ionization probability for protonated molecular ions within the first 10 nm due to the generation of free protons within the sample. Moreover, there is a 50% increase in fragment ion signal relative to steady state values 25 nm before reaching the guanine/Ag interface as a result of interfacial chemical damage accumulation. An altered layer thickness of 20 nm is observed as a consequence of ion beam induced chemical mixing. In general, we show that the neutral component of a molecular depth profile using the strong-field photoionization technique can be used to elucidate the effects of variations in ionization probability on the yield of molecular ions as well as to aid in obtaining accurate information about depth dependent chemical composition that cannot be extracted from TOF-SIMS data alone.

Polycystic liver disease and liver transplantation: single-institution experience.

Adult polycystic liver disease (PLD) can cause massive hepatomegaly leading to pain, caval obstruction, and hemorrhage. Many surgical techniques including aspiration, fenestration, and resection have been used to treat PLD. In addition to substantial morbidity and mortality, conservative surgery may have limited success, and palliation may be temporary. With improved results of liver transplantation, it has become the definitive treatment for PLD. We retrospectively reviewed our experience in patients with PLD between 1998 and 2007. Thirteen patients underwent liver only or liver-kidney transplantation. All surgical procedures were performed with preservation of the recipient inferior vena cava and without venovenous bypass (piggyback technique). Our patients experienced a high rate of perioperative morbidity. However, long-term patient and graft survival were excellent.

Strong-field ionization of sputtered molecules for biomolecular imaging.

Photoionization of molecules sputtered from molecular thin films has been achieved using high field 125 fs pulses in the mid-IR spectral range. Using several model systems, we show that it is possible to significantly reduce molecular fragmentation induced by the laser field by increasing the photoionization wavelength. By examining the photoionization spectra as a function of wavelength, it is apparent that the photoionization mechanism is changing from a non-adiabatic multi-electron excitation process to a process that involves tunnel ionization. The results of these observations are discussed in terms of their significance for bioimaging with focused ion beams and mass-spectrometry.

Kidney allocation to liver transplant candidates with renal failure of undetermined etiology: role of percutaneous renal biopsy.

The feasibility, value and risk of percutaneous renal biopsy (PRB) in liver transplant candidates with renal failure are unknown. PRB was performed on 44 liver transplant candidates with renal failure of undetermined etiology and glomerular filtration rate (GFR) <40 mL/min/1.73 m(2) (n = 37) or on renal replacement therapy (RRT) (n = 7). Patients with >or=30% interstitial fibrosis (IF), >or=40% global glomerulosclerosis (gGS) and/or diffuse glomerulonephritis were approved for simultaneous-liver-kidney (SLK) transplantation. Prebiopsy GFR, urinary sodium indices, dependency on RRT and kidney size were comparable between 27 liver-transplant-alone (LTA) and 17 SLK candidates and did not relate to the biopsy diagnosis. The interobserver agreement for the degree of IF or gGS was moderate-to-excellent. After a mean of 78 +/- 67 days, 16 and 8 patients received LTA and SLK transplants. All five LTA recipients on RRT recovered kidney function after transplantation and serum creatinine was comparable between LTA and SLK recipients at last follow-up. Biopsy complications developed in 13, of these, five required intervention. PRB is feasible in liver transplant candidates with renal failure and provides reproducible histological information that does not relate to the pretransplant clinical data. Randomized studies are needed to determine if PRB can direct kidney allocation in this challenging group of liver transplant candidates.

Neural substrates of intermanual transfer of a newly acquired motor skill.

In healthy humans, the two cerebral hemispheres show functional specialization to a degree unmatched in other animals, and such strong hemispheric specialization contributes to unimanual skill acquisition [1, 2]. When most humans learn a new motor skill with one hand, this process results in performance improvements in the opposite hand as well [3-6]. Despite the obvious adaptive advantage of such intermanual transfer, there is no direct evidence identifying the neural substrates of this form of skill acquisition [7-9]. Here, we used functional magnetic resonance imaging (fMRI) to study brain regions activated during intermanual transfer of a learned sequence of finger movements. First, we found that the supplementary motor area (SMA) has more activity when a skill has transferred well than when it has transferred poorly. Second, we found that fMRI activity in the ventrolateral posterior thalamic nucleus correlated with successful future intermanual transfer, whereas activity in the ventrolateral anterior thalamic nucleus correlated with past intermanual transfer. Third, we found that repetitive transcranial magnetic stimulation applied over the SMA blocked intermanual transfer without affecting skill acquisition. These findings provide direct evidence for an SMA-based mechanism that supports intermanual transfer of motor-skill learning.

Neural correlates of encoding and expression in implicit sequence learning.

In the domain of motor learning it has been difficult to separate the neural substrate of encoding from that of change in performance. Consequently, it has not been clear whether motor effector areas participate in learning or merely modulate changes in performance. Here, using a variant of the serial reaction time task that dissociated these two factors, we report that encoding during procedural motor learning does engage cortical motor areas and can be characterized by distinct early and late encoding phases. The highest correlation between activation and subsequent changes in motor performance was seen in the motor cortex during early encoding, and in the basal ganglia during the late encoding phase. Our results show that rapid encoding during procedural motor learning involves several distinct processes, and is represented primarily within motor system structures.

Probability detection mechanisms and motor learning.

The automatic detection of patterns or regularities in the environment is central to certain forms of motor learning, which are largely procedural and implicit. The rules underlying the detection and use of probabilistic information in the perceptual-motor domain are largely unknown. We conducted two experiments involving a motor learning task with direct and crossed mapping of motor responses in which probabilities were present at the stimulus set level, the response set level, and at the level of stimulus-response (S-R) mapping. We manipulated only one level at a time, while controlling for the other two. The results show that probabilities were detected only when present at the S-R mapping and motor levels, but not at the perceptual one (experiment 1), unless the perceptual features have a dimensional overlap with the S-R mapping rule (experiment 2). The effects of probability detection were mostly facilitatory at the S-R mapping, both facilitatory and inhibitory at the perceptual level, and predominantly inhibitory at the response-set level. The facilitatory effects were based on learning the absolute frequencies first and transitional probabilities later (for the S-R mapping rule) or both types of information at the same time (for perceptual level), whereas the inhibitory effects were based on learning first the transitional probabilities. Our data suggest that both absolute frequencies and transitional probabilities are used in motor learning, but in different temporal orders, according to the probabilistic properties of the environment. The results support the idea that separate neural circuits may be involved in detecting absolute frequencies as compared to transitional probabilities.

Cerebellum activation associated with performance change but not motor learning.

The issue of whether the cerebellum contributes to motor skill learning is controversial, principally because of the difficulty of separating the effects of motor learning from changes in performance. We performed a functional magnetic resonance imaging investigation during an implicit, motor sequence-learning task that was designed to separate these two processes. During the sequence-encoding phase, human participants performed a concurrent distractor task that served to suppress the performance changes associated with learning. Upon removal of the distractor, participants showed evidence of having learned. No cerebellar activation was associated with the learning phase, despite extensive involvement of other cortical and subcortical regions. There was, however, significant cerebellar activation during the expression of learning; thus, the cerebellum does not contribute to learning of the motor skill itself but is engaged primarily in the modification of performance.

Becoming aware of motor skill.

Conscious processes have a complex relationship to skilled motor performance. Past work has shown that some types of motor skill can be learned without any contribution from conscious processes. New work indicates that if those unconscious processes are disabled, conscious processes might step in to make up for the deficit.

Motor learning of compatible and incompatible visuomotor maps.

Brain imaging studies demonstrate increasing activity in limb motor areas during early motor skill learning, consistent with functional reorganization occurring at the motor output level. Nevertheless, behavioral studies reveal that visually guided skills can also be learned with respect to target location or possibly eye movements. The current experiments examined motor learning under compatible and incompatible perceptual/motor conditions to identify brain areas involved in different perceptual-motor transformations. Subjects tracked a continuously moving target with a joystick-controlled cursor. The target moved in a repeating sequence embedded within random movements to block sequence awareness. Psychophysical studies of behavioral transfer from incompatible (joystick and cursor moving in opposite directions) to compatible tracking established that incompatible learning was occurring with respect to target location. Positron emission tomography (PET) functional imaging of compatible learning identified increasing activity throughout the precentral gyrus, maximal in the arm area. Incompatible learning also led to increasing activity in the precentral gyrus, maximal in the putative frontal eye fields. When the incompatible task was switched to a compatible response and the previously learned sequence was reintroduced, there was an increase in arm motor cortex. The results show that learning-related increases of brain activity are dynamic, with recruitment of multiple motor output areas, contingent on task demands. Visually guided motor sequences can be linked to either oculomotor or arm motor areas. Rather than identifying changes of motor output maps, the data from imaging experiments may better reflect modulation of inputs to multiple motor areas.

The role of taxonomies in the study of human memory.

The idea that memory is not unitary but is instead composed of multiple systems has a long history and has been debated with particular vigor in the last 20 years. Nevertheless, whether or not there are multiple memory systems remains unsettled. In this article, we suggest that psychologists wishing to classify memory can learn from biological systematics, the discipline that creates taxonomies of species. In so doing, we suggest that psychologists have made two assumptions in classifying memory: that features of memory are perfectly correlated, and that there is a straightforward mapping between taxonomy and theory. We argue that these assumptions are likely to be incorrect, but we also argue that there is a place for taxonomy in the study of memory. Taxonomies of memory are organizational schemes for data--they are descriptive, not explanatory--and so can inspire theory, although they cannot serve as theories themselves.

Effect of sex and joystick experience on pursuit tracking in adults.

Using a joystick, adults (n = 39 males, 40 females in Experiment 1; n = 35 males, 40 females in Experiment 2; and n = 18 males, 18 females in Experiment 3) performed a computerized pursuit tracking task. Contrary to previously reported findings, the males were not more accurate than the females when performance was adjusted for prior perceptual-motor experience. Although no sex differences were found in a speeded tracking task, in an inverted tracking task the males exhibited a significant performance advantage; that advantage remained after several blocks of practice. Because participants' performance was adjusted statistically for prior perceptual-motor experience, the male advantage in inverted tracking was not related to experience. Rather, more proficient inverted tracking performance was associated with higher 3-dimensional mental rotations scores. In sum, sex differences in normal pursuit tracking may be better explained by differences in perceptual-motor experience. Inverted tracking, however, may depend on proficiency with spatial transformations.

Implicit motor sequence learning is represented in response locations.

Previous work (Willingham, 1999) has indicated that implicit motor sequence learning is not primarily perceptual; that is, what is learned is not a sequence of stimuli. Still other work has indicated that implicit motor sequence learning is not specific to particular muscle groups or effectors. In the present work, we tested whether implicit motor sequence learning would be represented as a sequence of response locations. In Experiment 1, learning showed very poor transfer when the response locations were changed, even though the stimulus positions were unchanged. In Experiment 2, participants switched their hand positions at transfer, so that one group of participants pushed the same sequence of keys but used a different sequence of finger movements to do so, whereas another group pushed a different sequence of keys but used the same sequence of finger movements used at training. Knowledge of the sequence was shown at transfer only if the sequence of response locations was maintained, not the sequence of finger movements.

Two novel human RAB genes with near identical sequence each map to a telomere-associated region: the subtelomeric region of 22q13.3 and the ancestral telomere band 2q13.

Two closely related genes have been identified at 2q13 and 22q13.3. These genes show similarity to members of the RAB family of small GTPases. RABL2A and RABL2B differ by three conservative amino acid changes over a total of 228 residues. Both are expressed in all tissues tested. Northern analysis showed that a 2.5-kb transcript is expressed in all tissues tested while a 1.4-kb transcript is specifically expressed only in muscle. The size difference between these two transcripts is the result of differential splicing of an intron within the 3' UTR. RABL2B is located within the subtelomeric region of 22q13.3. RABL2A maps to 2q13, the site of an ancestral telomere fusion event, suggesting that it also may be a subtelomeric gene.