Aural myiasis in Ancient Rome: Celsus and the ear maggots.

OBJECTIVE: Although today there is extensive scientific literature on aural myiasis, a historical study of the subject has yet to appear. This short article reports the first description of aural myiasis in the Western medical literature. METHODS: Methods involved: (1) scholarship review of ear diseases within Ancient Greek and Roman medical texts (L'Année philologique); (2) linguistic analysis for text identification through the Library of Latin Texts, the Thesaurus Linguae Latinae and the Loeb Classical Library; and (3) translation of the Latin texts that described cases of aural myiasis with commentary. RESULTS: To our knowledge, the earliest case of aural myiasis in Latin medical literature is reported by the Roman encyclopaedist Celsus (first century CE). In his De Medicina, he describes cases of Wohlfahrtia magnifica maggot infestation of the ear and how to treat affected patients. CONCLUSION: Despite present advances in otology, we believe that much insight can still be gained from this ancient example of medical history in ear diseases. A more comparative analysis of the subject is to be considered in the future, which will provide more data from different cultures and times.

Planar Networks of Boron Triangles: Analogies to Benzene and Other Planar Aromatic Hydrocarbons.

The lowest energy structures for Bn species (n = 6 to 23 except for 20) observed experimentally in the gas phase with a mass spectrometer are planar networks of boron triangles. Such networks are considered to consist of trigonal planar sp2-hybridized boron atoms having perpendicular p orbitals similar to the carbon atoms in benzene and other planar aromatic hydrocarbons. Electron bookkeeping for reasonable chemical bonding topologies of wheel-like structures such as B@Bn-1 (n = 6-9) leads to two π-electrons for B6 and B7+ similar to the cyclopropenyl cation and six π-electrons for B82- and B9- similar to benzene. Related chemical bonding topology analyses for low-energy oval B10 and B11- structures as well as for larger planar boron triangle networks with 12, 13, and 14 boron atoms suggest six π-electrons in such structures. Planar networks of boron triangles having 16-19 boron atoms are shown to be systems with 10 π-electrons similar to naphthalene. Similarly, low-energy planar B22 and B23- structures are shown to be 4 π-electron systems 1analogous to linear anthracene and angular phenanthrene, respectively. Intermediate B15- and B21- systems are shown to be systems with 4k rather than 4k + 2 π-electrons with 8 and 12 π-electrons, respectively. Structures based on planar networks of boron triangles are strongly energetically disfavored for B20 relative to a nonplanar decagonal antiprism structure with ideal D10d symmetry.

Boron monoxide dimer as a building block for boroxine based buckyballs and related cages: a theoretical study.

B3LYP/DZP level calculations are used to predict B2O2 cage oligomers, which are constructed from polyhedra by locating their B-B bonds at edge midpoints and three oxygen atoms at each degree 3 vertex. The stability of such cage oligomers depends highly on the B2nOn (n = 3, 4, 5) cavities corresponding to the polyhedral faces. All such polyhedral oligomers are found to have larger cohesive energies (Ec's) than corresponding planar structures, except for the smallest (B2O2)6 tetrahedron with extremely high strain arising from the four B6O3 cavities forming the tetrahedron faces. Promising (B2O2)n cages with the highest cohesive energies include pentagonal dodecahedral (B2O2)30 (c-B30) with B10O5 cavities, truncated octahedral (B2O2)36 (t-B36-2) with B8O4 cavities, and truncated icosahedral (B2O2)90 (t-B90) with B10O5 cavities. However, smaller (B2O2)n oligomers are also expected to exhibit cage structures having B8O4 or even B6O3 cavities because of their large Ec(s).

Time-resolved dosimetric verification of respiratory-gated radiotherapy exposures using a high-resolution 2D ionisation chamber array.

The aim of this work was to track and verify the delivery of respiratory-gated irradiations, performed with three versions of TrueBeam linac, using a novel phantom arrangement that combined the OCTAVIUS(®) SRS 1000 array with a moving platform. The platform was programmed to generate sinusoidal motion of the array. This motion was tracked using the real-time position management (RPM) system and four amplitude gating options were employed to interrupt MV beam delivery when the platform was not located within set limits. Time-resolved spatial information extracted from analysis of x-ray fluences measured by the array was compared to the programmed motion of the platform and to the trace recorded by the RPM system during the delivery of the x-ray field. Temporal data recorded by the phantom and the RPM system were validated against trajectory log files, recorded by the linac during the irradiation, as well as oscilloscope waveforms recorded from the linac target signal. Gamma analysis was employed to compare time-integrated 2D x-ray dose fluences with theoretical fluences derived from the probability density function for each of the gating settings applied, where gamma criteria of 2%/2 mm, 1%/1 mm and 0.5%/0.5 mm were used to evaluate the limitations of the RPM system. Excellent agreement was observed in the analysis of spatial information extracted from the SRS 1000 array measurements. Comparisons of the average platform position with the expected position indicated absolute deviations of <0.5 mm for all four gating settings. Differences were observed when comparing time-resolved beam-on data stored in the RPM files and trajectory logs to the true target signal waveforms. Trajectory log files underestimated the cycle time between consecutive beam-on windows by 10.0 ± 0.8 ms. All measured fluences achieved 100% pass-rates using gamma criteria of 2%/2 mm and 50% of the fluences achieved pass-rates >90% when criteria of 0.5%/0.5 mm were used. Results using this novel phantom arrangement indicate that the RPM system is capable of accurately gating x-ray exposure during the delivery of a fixed-field treatment beam.

Discovery of a silicon-based ferrimagnetic wheel structure in V(x)Si(12)(-) (x = 1-3) clusters: photoelectron spectroscopy and density functional theory investigation.

Our studies show that VSi(12)(-) adopts a V-centered hexagonal prism with a singlet spin state. The addition of the second V atom leads to a capped hexagonal antiprism for V(2)Si(12)(-) in a doublet spin state. Most interestingly, V(3)Si(12)(-) exhibits a ferrimagnetic, bicapped hexagonal antiprism wheel-like structure with a total spin of 4 µ(B).

Investigation into the radiobiological consequences of pre-treatment verification imaging with megavoltage X-rays in radiotherapy.

OBJECTIVE: The aim of this study was to investigate the effect of pre-treatment verification imaging with megavoltage X-rays on cancer and normal cell survival in vitro and to compare the findings with theoretically modelled data. Since the dose received from pre-treatment imaging can be significant, the incorporation of this dose at the planning stage of treatment has been suggested. METHODS: The impact of imaging dose incorporation on cell survival was investigated by clonogenic assay of irradiated DU-145 prostate cancer, H460 non-small-cell lung cancer and AGO-1522b normal tissue fibroblast cells. Clinically relevant imaging-to-treatment times of 7.5 and 15 min were chosen for this study. The theoretical magnitude of the loss of radiobiological efficacy due to sublethal damage repair was investigated using the Lea-Catcheside dose protraction factor model. RESULTS: For the cell lines investigated, the experimental data showed that imaging dose incorporation had no significant impact on cell survival. These findings were in close agreement with theoretical results. CONCLUSION: For the conditions investigated, the results suggest that allowance for the imaging dose at the planning stage of treatment should not adversely affect treatment efficacy. ADVANCES IN KNOWLEDGE: There is a paucity of data in the literature on imaging effects in radiotherapy. This article presents a systematic study of imaging dose effects on cancer and normal cell survival, providing both theoretical and experimental evidence for clinically relevant imaging doses and imaging-to-treatment times. The data provide a firm foundation for further study into this highly relevant area of research.

The prevalence of couple infertility in the United States from a male perspective: evidence from a nationally representative sample.

Infertility is a couple-based fecundity impairment, although population level research is largely based upon information reported by female partners. Of the few studies focusing on male partners, most focus on the utilization of infertility services rather than efforts to estimate the prevalence and determinants of infertility as reported by male partners. Data from a nationally representative sample of men aged 15-44 years who participated in the 2002 National Survey of Family Growth (NSFG) were used to estimate the prevalence of infertility and determinants of longer time-to-pregnancy (TTP) using the novel current duration (CD) approach. Using backward recurrence time parametric survival methods, we estimated infertility prevalence (TTP > 12 months) and time ratios (TR) associated with TTP as derived from males' reported CD of their pregnancy attempt. The estimated prevalence of infertility was 12.0% (95% CI: 7.0, 23.2). Longer TTP was associated with older male age (35-45 vs. 17-24 years) (TR: 2.49; 95% CI: 1.03, 6.03), biological childlessness (TR: 1.53; 95% CI: 1.07, 2.19) and lack of health insurance (TR: 1.73; 95% CI: 1.02, 2.94) after controlling for the differences in couples' age and other socioeconomic factors. The prevalence of infertility based on male reporting is consistent with estimates of infertility in the US found in prospective cohort studies and CD studies based on female reporting. Our findings suggest that male partners can reliably inform about couple infertility. Interventions and services aimed at reducing couple infertility should include attention to male factors associated with longer TTP identified in this study.

An in vitro study of the radiobiological effects of flattening filter free radiotherapy treatments.

Flattening filter free (FFF) linear accelerators allow for an increase in instantaneous dose-rate of the x-ray pulses by a factor of 2-6 over the conventional flattened output. As a result, radiobiological investigations are being carried out to determine the effect of these higher dose-rates on cell response. The studies reported thus far have presented conflicting results, highlighting the need for further investigation. To determine the radiobiological impact of the increased dose-rates from FFF exposures a Varian Truebeam medical linear accelerator was used to irradiate two human cancer cell lines in vitro, DU-145 prostate and H460 non-small cell lung, with both flattened and FFF 6 MV beams. The fluence profile of the FFF beam was modified using a custom-designed Nylon compensator to produce a similar dose profile to the flattened beam (6X) at the cell surface but at a higher instantaneous dose-rate. For both cell lines there appeared to be no significant change in cell survival. Curve fitting coefficients for DU145 cells irradiated with constant average dose-rates were 6X: α = 0.09 ± 0.03, ß = 0.03 ± 0.01 and 6FFF: α = 0.14 ± 0.13, ß = 0.03 ± 0.02 with a significance of p = 0.75. For H460 cells irradiated with the same instantaneous dose-rate but different average dose-rate the fit coefficients were 6FFF (low dose-rate): α = 0.21 ± 0.11, 0.07 ± 0.02 and 6FFF (high dose-rate): α = 0.21 ± 0.16, 0.07 ± 0.03, with p = 0.79. The results indicate that collective damage behaviour does not occur at the instantaneous dose-rates investigated here and that the use of either modality should result in the same clinical outcome, however this will require further validation in vivo.

Implementation of phantom-less IMRT delivery verification using Varian DynaLog files and R/V output.

This study aims to evaluate the use of Varian radiotherapy dynamic treatment log (DynaLog) files to verify IMRT plan delivery as part of a routine quality assurance procedure. Delivery accuracy in terms of machine performance was quantified by multileaf collimator (MLC) position errors and fluence delivery accuracy for patients receiving intensity modulated radiation therapy (IMRT) treatment. The relationship between machine performance and plan complexity, quantified by the modulation complexity score (MCS) was also investigated. Actual MLC positions and delivered fraction of monitor units (MU), recorded every 50 ms during IMRT delivery, were extracted from the DynaLog files. The planned MLC positions and fractional MU were taken from the record and verify system MLC control file. Planned and delivered beam data were compared to determine leaf position errors with and without the overshoot effect. Analysis was also performed on planned and actual fluence maps reconstructed from the MLC control file and delivered treatment log files respectively. This analysis was performed for all treatment fractions for 5 prostate, 5 prostate and pelvic node (PPN) and 5 head and neck (H&N) IMRT plans, totalling 82 IMRT fields in ∼5500 DynaLog files. The root mean square (RMS) leaf position errors without the overshoot effect were 0.09, 0.26, 0.19 mm for the prostate, PPN and H&N plans respectively, which increased to 0.30, 0.39 and 0.30 mm when the overshoot effect was considered. Average errors were not affected by the overshoot effect and were 0.05, 0.13 and 0.17 mm for prostate, PPN and H&N plans respectively. The percentage of pixels passing fluence map gamma analysis at 3%/3 mm was 99.94 ± 0.25%, which reduced to 91.62 ± 11.39% at 1%/1 mm criterion. Leaf position errors, but not gamma passing rate, were directly related to plan complexity as determined by the MCS. Site specific confidence intervals for average leaf position errors were set at -0.03-0.12 mm for prostate and -0.02-0.28 mm for more complex PPN and H&N plans. For all treatment sites confidence intervals for RMS errors with the overshoot was set at 0-0.50 mm and for the percentage of pixels passing a gamma analysis at 1%/1 mm a confidence interval of 68.83% was set also for all treatment sites. This work demonstrates the successful implementation of treatment log files to validate IMRT deliveries and how dynamic log files can diagnose delivery errors not possible with phantom based QC. Machine performance was found to be directly related to plan complexity but this is not the dominant determinant of delivery accuracy.

Iron-centered ten-vertex germanium clusters: the ubiquity of low energy pentagonal prismatic structures with various skeletal electron counts.

One of the most significant recent developments (in 2009) is the discovery of the clusters M@Ge10(3-) (M = Fe, Co) in which the outer Ge10 polyhedron is a pentagonal prism rather than a deltahedral structure of the type predicted by the Wade-Mingos rules. Consistent with this experimental observation, density functional theory shows the lowest energy structures to be pentagonal prisms for the iron-centered clusters Fe@Ge10(z) in all nine charge states ranging from -5 to +3. This contrasts with the previously studied cobalt-centered germanium clusters Co@Ge10(z) for which the lowest energy structures are pentagonal prisms only for the electron richest systems where z ranges from -3 to -5. The C3v structures derived from the tetracapped trigonal prism found as lowest energy structures of the electron poorer Co@Ge10(z) (z = 0, -1, -2) systems are higher energy structures for the iron-centered germanium clusters Fe@Ge10(z) (z = 0, -1, -2). The strong energetic preference for pentagonal prismatic structures in the Fe@Ge10(z) clusters can be attributed to the need for the larger volume of the pentagonal prism relative to other 10-vertex closed polyhedra to accommodate the interstitial iron atom.

Endohedral beryllium atoms in germanium clusters with eight and fewer vertices: how small can a cluster be and still encapsulate a central atom?

Structures of the beryllium-centered germanium clusters Be@Ge(n)(z) (n = 8, 7, 6; z = -4, -2, 0, +2) have been investigated by density functional theory to provide some insight regarding the smallest metal cluster that can encapsulate an interstitial atom. The lowest energy structures of the eight-vertex Be@Ge(8)(z) clusters (z = -4, -2, 0, +2) all have the Be atom at the center of a closed polyhedron, namely, a D(4d) square antiprism for Be@Ge(8)(4-), a D(2d) bisdisphenoid for Be@Ge(8)(2-), an ideal O(h) cube for Be@Ge(8), and a C(2v) distorted cube for Be@Ge(8)(2+). The Be-centered cubic structures predicted for Be@Ge(8) and Be@Ge(8)(2+) differ from the previously predicted lowest energy structures for the isoelectronic Ge(8)(2-) and Ge(8). This appears to be related to the larger internal volume of the cube relative to other closed eight-vertex polyhedra. The lowest energy structures for the smaller seven- and six-vertex clusters Be@Ge(n)(z) (n = 7, 6; z = -4, -2, 0, +2) no longer have the Be atom at the center of a closed Ge(n) polyhedron. Instead, either the Ge(n) polyhedron has opened up to provide a larger volume for the Be atom or the Be atom has migrated to the surface of the polyhedron. However, higher energy structures are found in which the Be atom is located at the center of a Ge(n) (n = 7, 6) polyhedron. Examples of such structures are a centered C(2v) capped trigonal prismatic structure for Be@Ge(7)(2-), a centered D(5h) pentagonal bipyramidal structure for Be@Ge(7), a centered D(3h) trigonal prismatic structure for Be@Ge(6)(4-), and a centered octahedral structure for Be@Ge(6). Cluster buildup reactions of the type Be@Ge(n)(z) + Ge(2) → Be@Ge(n+2)(z) (n = 6, 8; z = -4, -2, 0, +2) are all predicted to be highly exothermic. This suggests that interstitial clusters having an endohedral atom inside a bare post transition element polyhedron with eight or fewer vertices are less than the optimum size. This is consistent with the experimental observation of several types of 10-vertex polyhedral bare post transition element clusters with interstitial atoms but the failure to observe such clusters with external polyhedra having eight or fewer vertices.

Cobalt-centered ten-vertex germanium clusters: the pentagonal prism as an alternative to polyhedra predicted by the Wade-Mingos rules.

One of the most exciting recent (2009) discoveries in metal cluster chemistry is the pentagonal prismatic Co@Ge(10)(3-) ion, found in [K(2,2,2-crypt)](4)[Co@Ge(10)][Co(1,5-C(8)H(12))(2)]·toluene and characterized structurally by X-ray diffraction. The complete absence of triangular faces in the pentagonal prismatic structure of Co@Ge(10)(3-) contradicts expectations from the well-established Wade-Mingos rules, which predict polyhedral structures having mainly or entirely triangular faces. A theoretical study on Co@Ge(10)(z) systems (z = -5 to +1) predicts a singlet D(5h) pentagonal prismatic global minimum for the trianion Co@Ge(10)(3-) in accord with this experimental result. Redox reactions on this pentagonal prismatic Co@Ge(10)(3-) trianion generate low-energy pentagonal prismatic structures for Co@Ge(10)(z) where z = 0, -1, -2, -4, and -5 having quartet, triplet, doublet, doublet, and triplet spin states, respectively. Similar theoretical methods predict a singlet C(3v) polyhedral structure for the monoanion Co@Ge(10)(-), similar to previous theoretical predictions on the isoelectronic neutral Ni@Ge(10) and the structure realized experimentally in the isoelectronic Ni@In(10)(10-) found in the K(10)In(10)Ni intermetallic. Redox reactions on this C(3v) polyhedral Co@Ge(10)(-) monoanion generate low energy C(3v) polyhedral structures for Co@Ge(10)(z) where z = 0, -2, -3, and -4 having doublet, doublet, triplet, and quartet spin states, respectively.

LIAD-fs scheme for studies of ultrafast laser interactions with gas phase biomolecules.

Laser induced acoustic desorption (LIAD) has been used for the first time to study the parent ion production and fragmentation mechanisms of a biological molecule in an intense femtosecond (fs) laser field. The photoacoustic shock wave generated in the analyte substrate (thin Ta foil) has been simulated using the hydrodynamic HYADES code, and the full LIAD process has been experimentally characterised as a function of the desorption UV-laser pulse parameters. Observed neutral plumes of densities >10(9) cm(-3) which are free from solvent or matrix contamination demonstrate the suitability and potential of the source for studying ultrafast dynamics in the gas phase using fs laser pulses. Results obtained with phenylalanine show that through manipulation of fundamental femtosecond laser parameters (such as pulse length, intensity and wavelength), energy deposition within the molecule can be controlled to allow enhancement of parent ion production or generation of characteristic fragmentation patterns. In particular by reducing the pulse length to a timescale equivalent to the fastest vibrational periods in the molecule, we demonstrate how fragmentation of the molecule can be minimised whilst maintaining a high ionisation efficiency.

A comb-sampling method for enhanced mass analysis in linear electrostatic ion traps.

In this paper an algorithm for extracting spectral information from signals containing a series of narrow periodic impulses is presented. Such signals can typically be acquired by pickup detectors from the image-charge of ion bunches oscillating in a linear electrostatic ion trap, where frequency analysis provides a scheme for high-resolution mass spectrometry. To provide an improved technique for such frequency analysis, we introduce the CHIMERA algorithm (Comb-sampling for High-resolution IMpulse-train frequency ExtRAaction). This algorithm utilizes a comb function to generate frequency coefficients, rather than using sinusoids via a Fourier transform, since the comb provides a superior match to the data. This new technique is developed theoretically, applied to synthetic data, and then used to perform high resolution mass spectrometry on real data from an ion trap. If the ions are generated at a localized point in time and space, and the data is simultaneously acquired with multiple pickup rings, the method is shown to be a significant improvement on Fourier analysis. The mass spectra generated typically have an order of magnitude higher resolution compared with that obtained from fundamental Fourier frequencies, and are absent of large contributions from harmonic frequency components.

Endohedral beryllium atoms in ten-vertex germanium clusters: effect of a small interstitial atom on the cluster geometry.

Ten-vertex clusters are unusually versatile because polyhedra with 3-, 4-, and 5-fold symmetry are possible and are found in experimentally known structures. Such clusters therefore provide useful probes for subtle effects on cluster structure such as changing the electron count or introducing an interstitial atom. In this connection, DFT shows that one of the smallest possible interstitial atoms, namely beryllium, has relatively little effect on the structures of Be@Ge(10)(z) (z = +2, 0, -2, -4) clusters. Thus the same C(3v) and D(4d) polyhedra are found as the lowest energy structures for the isoelectronic pairs Be@Ge(10)(2+)/Ge(10) and Be@Ge(10)/Ge(10)(2-). Even for the more complicated potential energy surfaces of the Be@Ge(10)(2-)/Ge(10)(4-) and Be@Ge(10)(4-)/Ge(10)(6-) systems, the lowest energy structures are remarkably similar. Thus the same C(2v) structures are the global minima for both Be@Ge(10)(2-) and Ge(10)(4-). Similarly, the same slipped pentagonal prism structures are the global minima for both Be@Ge(10)(4-) and Ge(10)(6-).

Controlled redistribution of vibrational population by few-cycle strong-field laser pulses.

The use of strong-field (i.e. intensities in excess of 10(13) Wcm(-2)) few-cycle ultrafast (durations of 10 femtoseconds or less) laser pulses to create, manipulate and image vibrational wavepackets is investigated. Quasi-classical modelling of the initial superposition through tunnel ionization, wavepacket modification by nonadiabatically altering the nuclear environment via the transition dipole and the Stark effect, and measuring the control outcome by fragmenting the molecule is detailed. The influence of the laser intensity on strong-field ultrafast wavepacket control is discussed in detail: by modifying the distribution of laser intensities imaged, we show that focal conditions can be created that give preference to this three-pulse technique above processes induced by the pulses alone. An experimental demonstration is presented, and the nuclear dynamics inferred by the quasi-classical model discussed. Finally, we present the results of a systematic investigation of a dual-control pulse scheme, indicating that single vibrational states should be observable with high fidelity, and the populated state defined by varying the arrival time of the two control pulses. The relevance of such strong-field coherent control methods to the manipulation of electron localization and attosecond science is discussed.

The unique palladium-centered pentagonal antiprismatic cationic bismuth cluster: a comparison of related metal-centered 10-vertex pnictogen cluster structures by density functional theory.

Structures for the metal-centered 10-vertex pnictogen clusters M@Pn(10)(4+) (M = Ni, Pd, Pt; Pn = As, Sb, Bi) based on polyhedra with 3-fold, 4-fold, and 5-fold symmetry have been studied by density functional theory. Among these nine M/Pn combinations, only Pd@Bi(10)(4+) and Pt@Bi(10)(4+) are predicted to have the D(5d) pentagonal antiprism as the lowest energy structure in accord with experimental observation of this cluster in the ternary halide Bi(14)PdBr(10) as well as the prediction of the Wade-Mingos rules for these arachno systems. The lowest energy structures for the arsenic and antimony clusters M@Pn(10)(4+) (Pn = As, Sb) and Ni@Bi(10)(4+) are predicted to have structures derived from a tetracapped trigonal prism that has been severely distorted for M@As(10)(4+) (M = Pd, Pt). The volumes of the As(10) polyhedra other than the pentagonal prism are too small to contain interstitial palladium or platinum atoms so that major distortions are predicted for such clusters leading to partial opening of the polyhedron.

Endohedral nickel, palladium, and platinum atoms in 10-vertex germanium clusters: competition between bicapped square antiprismatic and pentagonal prismatic structures.

Density functional theory predicts significant differences in the preferred structures of endohedral M@Ge10z (M = Ni, Pd, Pt; z = 0, 2-, 4-) clusters upon a change of the central metal atom in otherwise isoelectronic systems. For the neutral clusters M@Ge10 the global minima are singlet bicapped square antiprisms. However, triplet regular pentagonal prismatic structures become increasingly energetically competitive in the series Ni --> Pd -> Pt. The pentagonal prismatic dianions M@Ge10(2-) (M = Ni, Pd, Pt) appear to have closed shell structures and are the global minima for palladium and platinum. However, the global minimum for Ni@Ge102- is the capped square antiprism suggested by the Wade-Mingos rules. A number of singlet low-energy unsymmetrical structures are found for the tetraanions M@Ge10(4-). However, for the palladium and platinum tetraanions triplet pentagonal prismatic structures are energetically competitive with the unsymmetrical structures.

The role of "external" lone pairs in the chemical bonding of bare post-transition element clusters: the Wade-Mingos rules versus the jellium model.

The jellium sphere model of a volume of electrons, counterbalanced by a positive charge throughout the sphere, leads to an energy level sequence corresponding to special stabilities of bare post-transition element clusters with 20 valence electrons such as the known P4 and clusters with 40 valence electrons such as the known Ge9(4-), Ni@In10(10-), and In11(7-). In this model the otherwise "external" lone pairs on the vertex atoms participate at least indirectly in the skeletal bonding. Furthermore, this model predicts the most favorable polyhedra and electron counts in some cases to be quite different than those predicted by the Wade-Mingos rules of polyhedral borane chemistry.

Temporal and spatial patterns of contaminants in Lake Erie watersnakes (Nerodia sipedon insularum) before and after the round goby (Apollonia melanostomus) invasion.

Temporal and spatial trends in contaminant concentrations were assessed in Lake Erie watersnakes, a threatened (USA)/endangered (Canada) species restricted to western Lake Erie. Temporal changes in plasma contaminant levels were determined in 1990 and 2003, and spatial patterns in 2003 at 12 sites, throughout the species' range. During this period, the watersnakes' diet changed from fish (75%) and amphibians (25%) that avoid zebra mussels, to round gobies (95%) that feed extensively on zebra mussels. Temporal trends indicate that watersnakes on Pelee and North Bass Islands showed a marginal increase in hexachlorobenzene levels, and a significant decline in dieldrin, oxychlordane, and heptachlor epoxide, likely reflecting declines in aerial deposition and clearing of local vineyards. The contaminants with the greatest burdens, sum PCBs and p,p'-DDE, remained stable in the snakes, consistent with trends in other local biota, suggesting that although the dietary switch to round gobies meant consumption of a more contaminated diet, their diet remained at the same trophic position. We suggest that the watersnakes' PCB and p,p'-DDE temporal patterns reflect the lack of change in sediment concentrations with minimal influence from their dietary switch. Similar to top avian predators, PCBs, p,p'-DDE, and technical chlordane, are most prevalent in watersnakes; this ranking remains unchanged. In 2003, the watersnakes demonstrated significant spatial differences in concentrations of p,p'-DDE, dieldrin, technical chlordane and its metabolites. Their 2003 concentrations of p,p'-DDE, and to a lesser extent PCBs, exceed the recommended interim no-observable effects levels on watersnake embryonic survival. Further investigations are required to determine if these higher levels of PCBs, p,p'-DDE, and technical chlordane, affect reproductive and physiological parameters of the Lake Erie watersnake. Until concentrations of sediment contaminants decline in western Lake Erie, these endangered/threatened watersnakes will continue to be exposed to higher concentrations of persistent organic pollutants.