The extent and nature of covalency in actinide complexes is an important and complex question. There are two main mechanisms of covalency, namely overlap of orbitals or degeneracy of the energies of the ligand and actinide metal, and computational approaches can play a significant part in rationalising the relative importance of each. In this work, we use a suite of computational approaches including Natural Bond Orbitals (NBO), Quantum Theory of Atoms in Molecules (QTAIM) and Interacting Quantum Atoms (IQA) to probe these effects in [E[double bond, length as m-dash]U[double bond, length as m-dash]E]2+ (E = O, S, Se, Te) and [UE2(H2O)5]2+ compounds. All methods indicate increased bond order and reduced charge separation on descending the group. Donation from filled np orbitals on E into formally empty orbitals on U is evident, with 5f and 6d orbitals the most populated. NBO analysis quantifies orbital interactions, finding energy separation is largest for E = O, while for E = Te the atomic orbitals are almost degenerate. However, NBO and IQA data suggests that although overlap is greater for heavier chalcogens, stabilisation due to covalency is greatest for E = O. Thus, for the heavier chalcogens we find that covalency is driven by near-degeneracy of orbitals involved, which does not stabilise the complexes to the same extent as overlap-driven covalency in uranyl. In the hydrated ions the same trends are broadly reproduced, albeit with more stabilisation and a lower HOMO-LUMO gap. The structure and stability of the [O[double bond, length as m-dash]U[double bond, length as m-dash]S]2+ ion is also examined, showing evidence for an inverse trans-influence. Finally bending of the [US2(H2O)5]2+ ion has been examined, suggesting a possible meta-stable cis-form.

Studtite, [UO2(η2-O2)(H2O)2]·2H2O, and metastudtite, [UO2(η2-O2)(H2O)2], are important phase alterations of UO2 in a spent nuclear fuel repository and have previously been shown to react with Np(v). In this work we extend the study to Am(v) on a tracer scale and show spectroscopic evidence that the Am is incorporated into the structure of studtite as Am(iii). A computational study on the possible mechanisms for the incorporation of Np and Am shows that protonation of the -yl oxygen is the favoured route and the calculated incorporation energies are large and positive. The results suggest that Am is less favoured compared to Np but energetically more favoured to incorporate both actinide ions into metastudtite rather than studtite. Finally, we have shown that once incorporated, Am readily leaches into water but spectroscopic measurements suggest subtle changes in the structure of studtite.

Oxidation of Cs4[U(NCS)8] in MeCN or DMF affords structurally characterised examples of the mixed-valent UIV/VI compound Cs14[{U(NCS)8}3{UO2(NCS)4(H2O)}]·4.5H2O, or the [UIV-UV-UIV][UVI] species [U(DMF)8(μ-O)U(NCS)5(μ-O)U(DMF)7(NCS)][UO2(NCS)5]. Vibrational and magnetism data support their oxidation state formulism, which is further corroborated by computational methodology.

Neptunium(V) and uranium(VI) are precipitated from an aqueous potassium-sodium-containing carbonate-rich solution, and the solid phases are investigated. U/Np M4,5-edge high-energy resolution X-ray absorption near edge structure (HR-XANES) spectroscopy and Np 3d4f resonant inelastic X-ray scattering (3d4f RIXS) are applied in combination with thermodynamic calculations, U/Np L3-edge XANES, and extended X-ray absorption fine structure (EXAFS) studies to analyze the local atomic coordination and oxidation states of uranium and neptunium. The XANES/HR-XANES analyses are supported by ab initio quantum-chemical computations with the finite difference method near-edge structure code (FDMNES). The solid precipitates are also investigated with powder X-ray diffraction, scanning electron microscopy-energy dispersive X-ray spectroscopy, and Raman spectroscopy. The results strongly suggest that K[NpVO2CO3](cr), K3[NpVO2(CO3)2](cr), and K3Na[UVIO2(CO3)3](cr) are the predominant neptunium and uranium solid phases formed. Despite the 100 times lower initial neptunium(V) concentration at pH 10.5 and oxic conditions, neptunium(V)-rich phases predominately precipitate. The prevailing formation of neptunium(V) over uranium(VI) solids demonstrates the high structural stability of neptunium(V) carbonates containing potassium. It is illustrated that the Np M5-edge HR-XANES spectra are sensitive to changes of the Np-O axial bond length for neptunyl(V/VI).

HISTORY: This is a case of an otherwise healthy 19-year-old running back who sustained a left ankle eversion type injury during a football game when an opponent landed on his lower leg forcing it into external rotation. He did not finish playing due to the inability to bear weight. PHYSICAL EXAMINATION: During initial evaluation, limited due to a significant amount of pain, he had tenderness over the deltoid, anterior talofibular, and calcaneofibular ligaments. During reevaluation two days later he was also complaining of some tenderness around the lateral aspect of his left knee. His exam showed mild edema at the level of his ankle, tenderness over ligaments as noted before, along with pain on external rotation of his foot, compression along his syndesmosis, and palpation over his tibiofibular joint with increased posterior translation of his proximal fibula compared to the contralateral side. His left knee exam revealed pain in the area of his fibular head with varus stress, but was otherwise unremarkable. DIFFERENTIAL DIAGNOSIS: Ankle fracture Syndesmosis injury Proximal tibiofibular joint injury TEST AND RESULTS: Stress radiographs of left ankle at the stadium: - no acute fracture and no obvious opening of his syndesmosis or medial joint space Repeat weight bearing radiographs of left ankle: - ossification of his syndesmosis likely indicative of previous injury, as well as decreased overlap between distal tibia and fibula - no clear evidence of medial ankle joint space widening MRI of left calf and ankle: - no ligamentous tear of the proximal tibiofibular joint, but changes consistent with chronic avulsion injury of the syndesmotic membrane from the distal portion of the tibia and probable injuries to his anterior inferior tibiofibular ligament and anterior talofibular ligaments FINAL WORKING DIAGNOSIS: Syndesmosis injury with proximal tibiofibular joint instability TREATMENT AND OUTCOMES: 1. Non-weightbearing for the initial 10 days post injury. 2. Open reduction and internal fixation of distal syndesmosis using a single tightrope fixation, along with stabilization of the proximal tibiofibular joint using the same technique. 3. Non-weightbearing for the following 6 weeks. 4. Gradual return to physical activity.

The purpose of this qualitative study was to indicate the experiences of collegiate student-athletes in meeting academic demands when experiencing prolonged recovery from concussion and if they perceive a need for academic accommodations. There is a gap in present concussion and an absence of studies that examine if academic accommodations are helpful during concussion recovery. The study was guided by 3 research questions focused on the return to learn during the recovery process. The study was limited to 9 student-athletes currently enrolled at three postsecondary institutions: Christian Brothers University, Rhodes College, and the University of Memphis. The study participants met pre-established criteria for the study, were recruited by their athletic trainer at their respective institution, and voluntarily participated in individual interviews with the researcher or co-interviewer. Through a phenomenological approach, individual interviews were conducted with the participants. Four themes were identified in the data: negative impact on academic performance, academic pressures, inequity of student-athlete treatment, and impact on concentration ability. Each study participant’s story was shared through the data analysis process, and significant statements from the interviews as related to the research questions were included in the data analysis section. Ultimately, the data suggested that future research continue to focus on how student-athletes' recovery from concussion impacts their return to learn process.

The solid-state structures of CF3(CF2)(5)CH2CO2H and a fluorous triazole are reported, both of which display a wide variety and large number of noncovalent interactions in their packing. The solid-state structure of CF3(CF2)(5)CH2CO2H is stabilized by multiple F...F contacts but only one CH...FC interaction, as well as O-H...O and C-H...O hydrogen bonds. In contrast to other reported structures, the torsion angles in the fluorous chain are close to 180 degrees, which means that the fluorine atoms are eclipsed. A DFT study of the interactions in both compounds show that F...F interactions, along with stacking and C-H...F and C-H...O contacts, are individually weakly energetically stabilizing, but collectively, they can give rise to interaction energies of up to 13 kcal mol(-1). A topological approach to the interactions using atoms-in-molecules (AIM) theory reveals that there are bond critical points between the C-F...F-C interactions as well as C-F...H-C interactions that are not recognized when using only the van der Waals distances.

New highly fluorinated monodentate and bidentate phosphine oxide compounds of the type {CF(3)(CF(2))(n)CH(2)CH(2)}(3)PO (n = 5, 9) and [{CF(3)(CF(2))(5)CH(2)CH(2)}(2)P(O)CH(2)CH(2)P(O){CH(2)CH(2)(CF(2))(5)CF(3)}] have been prepared. Their ability to extract a number of metals and radionuclides from aqueous solutions into perfluorinated solvents has been established and the extractable species investigated. All extractants extract the metals As(V), Cd(II), Co(II), Cr(VI), Hg(II), Pb(II), and Sn(II) with >75% removal. In addition, the radioisotopes (90)Sr(II), (133)Ba(II), and U(VI) have been investigated, whilst (59)Fe(III) has been used to model the extraction of plutonium. (133)Ba(II) shows a high distribution ratio for monodentate phosphine oxides, whilst for UO(2)(2+) and (59)Fe(III) bidentate phosphine oxides are superior.

ABSTRACT Optimal collection and preservation protocols for fecal DNA genotyping are not firmly established. We evaluated 3 factors that influence microsatellite genotyping success of fecal DNA extracted from coyote (Canis latrans) scats: 1) age of scat, 2) preservative, and 3) diet content. We quantified genotyping success by comparing rates of allelic dropout, false alleles, and failed amplifications among consensus genotypes. We used a panel of 6 microsatellite loci to genotype 20 scat samples, each of which was subjected to 3 age (1 day, 5 days, and 10 days post-deposition) and 3 preservation (DET buffer, 95% ethanol [EtOH], and lysis buffer) treatments. Both sample age and storage buffer had a significant effect on success and reliability. Ethanol and DET buffer preserved fecal samples with similar efficiency, and both were superior to lysis buffer. Our analysis of DNA degradation rates revealed that samples collected as early as 5 days of age yielded DNA that was highly degraded relative to samples collected on day 1. We tested the influence of dietary remains on microsatellite genotyping by using scat samples consisting predominantly of insect prey (n = 5), mammalian prey (n = 9), or the remains of juniper (Juniperus spp.) berries (n = 6) and compared EtOH and DET buffer preservation efficacy. We observed a significant interaction effect between storage buffer and diet for the probability of a false allele in a polymerase chain reaction (PCR), suggesting that the optimal preservation technique depended on the food remains comprising the scat. Scats comprised of juniper berry remains were more reliably genotyped when preserved in DET than EtOH. Mammalian preybased scats were more reliable when stored in EtOH than DET buffer. Insect-predominant scats were preserved in EtOH and DET buffer with similar efficiency. Although accurate and reliable results can be obtained from scats collected at ≥5 days of age, we suggest sampling design to include collection of scats <5 days of age to minimize field and laboratory expenses. We suggest EtOH preservation for scats of obligate carnivores and of facultative carnivores with a diet consisting primarily of mammals. We suggest DET buffer preservation for animals with a diet consisting of plant-derived foods. Lysis buffer protocols that we employed should not be used for fecal DNA preservation.

HISTORY: 19 year old freshman college defensive lineman sustained helmet to helmet contact during practice. There was no loss of consciousness. He was found wandering the sidelines where he complained of headache and nausea with subsequent vomiting. He did not know his name, current location, nor date and place of birth. Previous concussion with overnight hospital say with full recovery in 1 week. No neurological problems in the family. No tobacco, alcohol or drug use. No history of migraines, headaches, depression, learning disabilities PHYSICAL EXAMINATION General: awake, but not alert to person, place or time. GCS 14 out of 16, no physical injuries, able to move all extremities HEENT: no head deformity or skull tenderness, no cervical spine/paraspinal tenderness, full active and passive range of motion of neck Neurological: General: awake, able to follow commands with poor reaction time, cooperative. Aware of first name but not last name, not alert to place, position, or time Cranial Nerves: PERLA, extraocular movements intact, equal smile Strength: 5/5 upper & lower extremities Sensation: 100% upper & lower extremities Cerebellar: able to walk but unsteady, rapid alternating activity and finger tapping equal Reflexes: 2+ knees DIFFERENTIAL DIAGNOSIS: Concussion Intracranial bleed Subdural hematoma Epidural hematoma Maliganant brain edema Second impact syndrome (possible incidental previous head trauma) Diffuse axonal injury TEST AND RESULTS: CT cervical spine - No fracture, subluxation, disc extrusion CT brain without contrast - Normal MRI - Normal Neuropsychological evaluation - Abnormal, consistent with post concussive syndrome COURSE: Athlete was sent to the ER for further assessment and admitted with concussion to the neurovascular unit for observation and discharged the following day with recommendations to undergo an outpatient cognitive screen. One week later parents reports he is doing better and making progress with limitation of outside stimuli. Two weeks later he reports his is 85% better and athlete and parents decided to try and return to class. FINAL WORKING DIAGNOSIS: Concussion Post-concussion syndrome TREATMENT AND OUTCOMES: Occupational and speech therapy Monthly re-evaluations with neuropsychologist Evaluate return to play in 6 months Physical activity as tolerated

Abstract The extraction efficiency of some perfluorinated phenols for the removal of Cs+ and Sr2+ from aqueous solutions is reported. The perfluorinated phenols C6F5OH and 2,3,5,6-C6F4HOH have been shown to extract 90Sr2+ or Cs+ from aqueous solutions into a 100:1 mixture of toluene and pyridine in reasonable efficiencies, using radio-tracer and ICP-OES techniques. Additionally uranium, 59Fe3+ {as a model for Pu(IV)} and Eu3+ {as a model for Am(III)} were investigated, with only iron not being successfully extracted.

A ketone with perfluoroalkyl chains has been developed for the extraction of M(II) (M=Sn, Cd, Hg, Pb) and As(V) from aqueous and organic solvents under heterogeneous and homogeneous conditions using the unique thermomorphic properties of these ligands.

CONTEXTMany researchers have investigated the effectiveness of different types of cold application, including cold whirlpools, ice packs, and chemical packs. However, few have investigated the effectiveness of different types of ice used in ice packs, even though ice is one of the most common forms of cold application.OBJECTIVETo evaluate and compare the cooling effectiveness of ice packs made with cubed, crushed, and wetted ice on intramuscular and skin surface temperatures.DESIGNRepeated-measures counterbalanced design.SETTINGHuman performance research laboratory.PATIENTS OR OTHER PARTICIPANTSTwelve healthy participants (6 men, 6 women) with no history of musculoskeletal disease and no known preexisting inflammatory conditions or recent orthopaedic injuries to the lower extremities.INTERVENTION(S)Ice packs made with cubed, crushed, or wetted ice were applied to a standardized area on the posterior aspect of the right gastrocnemius for 20 minutes. Each participant was given separate ice pack treatments, with at least 4 days between treatment sessions.MAIN OUTCOME MEASURE(S)Cutaneous and intramuscular (2 cm plus one-half skinfold measurement) temperatures of the right gastrocnemius were measured every 30 seconds during a 20-minute baseline period, a 20-minute treatment period, and a 120-minute recovery period.RESULTSDifferences were observed among all treatments. Compared with the crushed-ice treatment, the cubed-ice and wetted-ice treatments produced lower surface and intramuscular temperatures. Wetted ice produced the greatest overall temperature change during treatment and recovery, and crushed ice produced the smallest change.CONCLUSIONSAs administered in our protocol, wetted ice was superior to cubed or crushed ice at reducing surface temperatures, whereas both cubed ice and wetted ice were superior to crushed ice at reducing intramuscular temperatures.

On 11 December 2007, the science of mammalogy lost one of its most valued and influential leaders. Terry Lamon Yates succumbed to complications of treatments for an aggressive form of brain cancer after a brief but courageous fight. He was born on 17 March 1950, in Mayfield, Kentucky, the oldest son of Ellen Wanda Byrd and William Hanley Yates. Terry's only sibling was a brother, Johnny. He is survived by his wife Nancy Fennell, his 2 sons Brian Christopher and Michael Ryan, and daughter-in-law Laura Mancheno Macia. Over the last 30 years, Terry, usually accompanied by Nancy, his bride of 36 years, attended all but 1 of the annual meetings of the American Society of Mammalogists (ASM). It was not uncommon to hear comments about how well Nancy and Terry enjoyed each other's company. Their relationship was special. Terry and Nancy 1st met when she was a junior in high school, and he was a freshman at Murray State University in Murray, Kentucky. Terry convinced Nancy, who lived in Houston, to attend Murray State, and they later married on 7 August 1971, when Terry was a senior and Nancy was a sophomore. Terry raised the money to buy Nancy's engagement ring by returning soft drink bottles collected from dorm trash cans, roadsides, and other places, and by running a trapline before class. Their oldest son, Brian, was born in Lubbock, Texas, on the night Terry passed his oral comprehensive exams for his Ph.D. Michael was born in New Mexico after Terry was a faculty member at the University of New Mexico. Terry's education as a biologist began with his bachelor's degree from Murray State University in 1972. Terry then completed his master's degree in biology from Texas A&M University in 1975, studying North American moles under the guidance of David …

The purpose of the study was to determine whether uniform intramuscular heating is achieved throughout a treatment area 2 times the transducer head at both 1 and 3 MHz. Seven male and three female subjects (Age: 23.6 ± 1.0 yrs, Weight: 83.8 ± 23.2 kg, Site Skinfold: 13.9 ± 7.3 mm) underwent two ultrasound treatments (1 and 3 MHz) in the triceps surae muscle group. Thermocouples were inserted at the midpoint and periphery of the treatment area. Ten minute baseline temperatures were recorded followed by a ten minute ultrasound treatment. Two (site) X 10 (time) repeated measures ANOVAs were separately used to determine significance for 1 and 3 MHz treatments. Post-hoc testing was performed using the Bonferroni adjustment. A significant site-by-time interaction was observed for both the 1 and 3 MHz treatments. From baseline to the end of the treatment, temperature increased approximately 2.62°C and 1.58°C for the midpoint and periphery of the 1 MHz treatment and 5.88°C and 3.64°C for the 3 MHz treatment. The differences in temperature suggest that uniform heating does not occur throughout the treatment area. Key points3 MHz is more effective in raising intramuscular temperature within ERA.Stroke count/rate of transducer may play a factor in heating tissue.Treatment size may alter uniform heating.

Rhogeëssa H. Allen, 1866:285. Type species Rhogeessa tumida H. Allen, 1866:286, by subsequent designation (Miller 1897). Rhogöessa Marschall, 1873:11. Incorrect subsequent spelling of Rhogeëssa H. Allen, 1866:285. Baeodon Miller, 1906:85. Type species Rhogeessa alleni Thomas, 1892:477, by original designation. Baedon Alvarez and Aviña, 1965. Incorrect subsequent spelling of Baeodon Miller, 1906:85.

The reactivity of several transition metal half sandwich complexes towards an anionic gallium(I) heterocyclic complex, [K(tmeda)][Ga{[N(Ar)C(H)]2}](Ar = C6H3Pri2-2,6), has been investigated. This has led to the anionic half sandwich complexes, [K(tmeda)][(C5H4R)M(CO)n[Ga{[N(Ar)C(H)]2}]](M = V, R = H, n= 3; M = Mn, R = Me, n= 2; M = Co, R = H, n= 1), which crystallographic studies show to form dimers (M = Mn and Co) or a polymer (M = V) through bridging potassium cations. The metal-gallium bond lengths in all complexes are very short which, combined with some spectroscopic evidence, is suggestive of M-Ga pi-bonding. Density functional theory studies of models of all complexes indicate that the level of back-bonding in these complexes is, however, minimal and of a similar order to that seen in analogous complexes incorporating neutral N-heterocyclic carbene ligands. Reactions of the metallocenes, [M(C5H4Me)2](M = V or Cr), with the digallane4, [Ga{[N(Ar)C(H)]2}]2, have afforded the neutral complexes, [M(C5H4Me)2[Ga{[N(Ar)C(H)]2}]], which are thought to be formed via an initial oxidative insertion of the transition metal centre into the Ga-Ga bond of the digallane. X-Ray crystallography shows the complexes to be monomeric. One (M = V) reacts with one equivalent of [K(tmeda)][Ga{[N(Ar)C(H)]2}] to give the crystallographically characterised, anionic bis(gallyl)-complex, [K(tmeda)][V(C5H4Me)2[Ga{[N(Ar)C(H)]2}]2]. For comparison, the reaction of [K(tmeda)][Ga{[N(Ar)C(H)]2}] with [Mn{CH(SiMe3)2}2] was carried out and gave the monomeric, anionic complex, [K(tmeda)][Mn{CH(SiMe3)2}2[Ga{[N(Ar)C(H)]2}]].

Bank vole, Clethrionomys glareolus, specimens have been annually sampled from the radioactive Chernobyl, Ukraine, environment and nonradioactive reference sites since 1997. Exposed voles continually exhibit increased mitochondrial DNA haplotype (h) and nucleotide diversity (ND), observed in the hypervariable control region (1997-1999). Increased maternal mutation rates, source-sink relationships, or both are proposed as hypotheses for these differences. Samples from additional years (2000 and 2001) have been incorporated into this temporal study. To evaluate the hypothesis that an increased mutation rate is associated with increased h, DNA sequences were examined in a phylogenetic context for novel substitutions not observed in haplotypes from bank voles from outside Ukraine or in other species of Clethrionomys. Such novel substitutions might result from in situ mutation events and. if largely restricted to samples from radioactive environments, support an increased maternal mutation rate in these areas. The only unique substitution meeting this criterion was found in an uncontaminated reference site. All other substitutions are found in other haplotypes of the bank vole or in other species. Increased maternal mutation rates do not appear to explain trends in h and ND observed in northern Ukraine. Studies examining ecological dynamics will clarify the reasons behind, and significance of, increased levels of h in contaminated areas.