190 research outputs found
Reactivity of a dititanium bis(pentalene) complex toward heteroallenes and main-group elementâelement bonds
The reactivity of the TiâTi double bond in (ÎŒ,η5:η5-Pnâ )2Ti2 (1; Pnâ = 1,4-{SiiPr3}2C8H4) toward isocyanide and heteroallene substrates, and molecules featuring homonuclear bonds between main-group elements (EâE) has been explored. Reaction of 1 with methyl isocyanide or 1,3-N,NâČ-di-p-tolylcarbodiimide resulted in the formation of the 1:1 adducts (ÎŒ,η5:η5-Pnâ )2Ti2(ÎŒ,η2-CNMe) (2) and (ÎŒ,η5:η5-Pnâ )2Ti2(ÎŒ-C{N(4-C6H4CH3)}2) (3), respectively, which are thermally stable up to 100 °C in contrast to the analogous adducts formed with CO and CO2. Reaction of 1 with phenyl isocyanate afforded a paramagnetic complex, [(η8-Pnâ )Ti]2(ÎŒ,Îș2:Îș2-O2CNPh) (4), in which the âdouble-sandwichâ architecture of 1 has been broken and an unusual phenyl-carbonimidate ligand bridges two formally Ti(III) centers. Reaction of 1 with diphenyl dichalcogenides, Ph2E2 (E = S, Se, Te), led to the series of TiâTi single-bonded complexes (ÎŒ,η5:η5-Pnâ )2[Ti(EPh)]2 (E = S (5), Se (6), Te (7)), which can be considered the result of a 2eâ redox reaction or a 1,2-addition across the TiâTi bond. Treatment of 1 with azobenzene or phenyl azide afforded [(η8-Pnâ )Ti]2(ÎŒ-NPh)2 (8), a bridging imido complex in which the pentalene ligands bind in an η8 fashion to each formally Ti(IV) center, as the result of a 4eâ redox reaction driven by the oxidative cleavage of the TiâTi double bond. The new complexes 2â8 were extensively characterized by various techniques including multinuclear NMR spectroscopy and single-crystal X-ray diffraction, and the experimental work was complemented by density functional theory (DFT) studies
Bridging the Mid-Infrared-to-Telecom Gap with Silicon Nanophotonic Spectral Translation
Expanding far beyond traditional applications in optical interconnects at
telecommunications wavelengths, the silicon nanophotonic integrated circuit
platform has recently proven its merits for working with mid-infrared (mid-IR)
optical signals in the 2-8 {\mu}m range. Mid-IR integrated optical systems are
capable of addressing applications including industrial process and
environmental monitoring, threat detection, medical diagnostics, and free-space
communication. Rapid progress has led to the demonstration of various silicon
components designed for the on-chip processing of mid-IR signals, including
waveguides, vertical grating couplers, microcavities, and electrooptic
modulators. Even so, a notable obstacle to the continued advancement of
chip-scale systems is imposed by the narrow-bandgap semiconductors, such as
InSb and HgCdTe, traditionally used to convert mid-IR photons to electrical
currents. The cryogenic or multi-stage thermo-electric cooling required to
suppress dark current noise, exponentially dependent upon the ratio Eg/kT, can
limit the development of small, low-power, and low-cost integrated optical
systems for the mid-IR. However, if the mid-IR optical signal could be
spectrally translated to shorter wavelengths, for example within the
near-infrared telecom band, photodetectors using wider bandgap semiconductors
such as InGaAs or Ge could be used to eliminate prohibitive cooling
requirements. Moreover, telecom band detectors typically perform with higher
detectivity and faster response times when compared with their mid-IR
counterparts. Here we address these challenges with a silicon-integrated
approach to spectral translation, by employing efficient four-wave mixing (FWM)
and large optical parametric gain in silicon nanophotonic wires
A scoping review of biopsychosocial risk factors and co-morbidities for common spinal disorders
OBJECTIVE: The purpose of this review was to identify risk factors, prognostic factors, and comorbidities associated with common spinal disorders.
METHODS: A scoping review of the literature of common spinal disorders was performed through September 2016. To identify search terms, we developed 3 terminology groups for case definitions: 1) spinal pain of unknown origin, 2) spinal syndromes, and 3) spinal pathology. We used a comprehensive strategy to search PubMed for meta-analyses and systematic reviews of case-control studies, cohort studies, and randomized controlled trials for risk and prognostic factors and cross-sectional studies describing associations and comorbidities.
RESULTS: Of 3,453 candidate papers, 145 met study criteria and were included in this review. Risk factors were reported for group 1: non-specific low back pain (smoking, overweight/obesity, negative recovery expectations), non-specific neck pain (high job demands, monotonous work); group 2: degenerative spinal disease (workers\u27 compensation claim, degenerative scoliosis), and group 3: spinal tuberculosis (age, imprisonment, previous history of tuberculosis), spinal cord injury (age, accidental injury), vertebral fracture from osteoporosis (type 1 diabetes, certain medications, smoking), and neural tube defects (folic acid deficit, anti-convulsant medications, chlorine, influenza, maternal obesity). A range of comorbidities was identified for spinal disorders.
CONCLUSION: Many associated factors for common spinal disorders identified in this study are modifiable. The most common spinal disorders are co-morbid with general health conditions, but there is a lack of clarity in the literature differentiating which conditions are merely comorbid versus ones that are risk factors. Modifiable risk factors present opportunities for policy, research, and public health prevention efforts on both the individual patient and community levels. Further research into prevention interventions for spinal disorders is needed to address this gap in the literature
Robust estimation of microbial diversity in theory and in practice
Quantifying diversity is of central importance for the study of structure,
function and evolution of microbial communities. The estimation of microbial
diversity has received renewed attention with the advent of large-scale
metagenomic studies. Here, we consider what the diversity observed in a sample
tells us about the diversity of the community being sampled. First, we argue
that one cannot reliably estimate the absolute and relative number of microbial
species present in a community without making unsupported assumptions about
species abundance distributions. The reason for this is that sample data do not
contain information about the number of rare species in the tail of species
abundance distributions. We illustrate the difficulty in comparing species
richness estimates by applying Chao's estimator of species richness to a set of
in silico communities: they are ranked incorrectly in the presence of large
numbers of rare species. Next, we extend our analysis to a general family of
diversity metrics ("Hill diversities"), and construct lower and upper estimates
of diversity values consistent with the sample data. The theory generalizes
Chao's estimator, which we retrieve as the lower estimate of species richness.
We show that Shannon and Simpson diversity can be robustly estimated for the in
silico communities. We analyze nine metagenomic data sets from a wide range of
environments, and show that our findings are relevant for empirically-sampled
communities. Hence, we recommend the use of Shannon and Simpson diversity
rather than species richness in efforts to quantify and compare microbial
diversity.Comment: To be published in The ISME Journal. Main text: 16 pages, 5 figures.
Supplement: 16 pages, 4 figure
Use of conventional and alternative treatment strategies for a case of low back pain in a F/A-18 aviator
BACKGROUND: Low back pain can diminish jet pilot concentration and function during flight and be severe enough to ground pilots or cause decreased flying time. The objective of this case report is to present an example of the integration of chiropractic care with conventional treatments for the management of low back pain in a F/A-18 aviator. CASE PRESENTATION: The patient had insidious severe low back pain without radiation or neurological deficit, resulting in 24 hours of hospitalization. Spinal degeneration was discovered upon imaging. Four months later, it still took up to 10 minutes for him to get out of bed and several minutes to exit the jet due to stiffness and pain. He had discontinued his regular Marine Corps fitness training due to pain avoidance. Pain severity ranged from 1.5â7.1 cm on a visual analog scale. His Roland Morris Disability Questionnaire score was 5 out of 24. The pilot's pain was managed with the coordinated efforts of the flight surgeon, physiatrist, physical therapist, and doctor of chiropractic. Following this regimen he had no pain and no functional disability; he was able to fly multiple training missions per week and exercise to Marine Corps standards. CONCLUSION: A course of care integrating flight medicine, chiropractic, physical therapy, and physiatry appeared to alleviate pain and restore function to this F/A-18 aviator with low back pain
Complex C: A Low-Metallicity High-Velocity Cloud Plunging into the Milky Way
(Abridged) We present a new high-resolution (7 km/s FWHM) echelle spectrum of
3C 351 obtained with STIS. 3C 351 lies behind the low-latitude edge of
high-velocity cloud Complex C, and the new spectrum provides accurate
measurements of O I, Si II, Al II, Fe II, and Si III absorption lines at the
velocity of the HVC. We use collisional and photoionization models to derive
ionization corrections; in both models we find that the overall metallicity Z =
0.1 - 0.3 Z_{solar} in Complex C, but nitrogen must be underabundant. The iron
abundance indicates that Complex C contains very little dust. The absorbing gas
probably is not gravitationally confined. The gas could be pressure-confined by
an external medium, but alternatively we may be viewing the leading edge of the
HVC, which is ablating and dissipating as it plunges into the Milky Way. O VI
column densities observed with FUSE toward nine QSOs/AGNs behind Complex C
support this conclusion: N(O VI) is highest near 3C 351, and the O VI/H I ratio
increases substantially with decreasing latitude, suggesting that the
lower-latitude portion of the cloud is interacting more vigorously with the
Galaxy. The other sight lines through Complex C show some dispersion in
metallicity, but with the current uncertainties, the measurements are
consistent with a constant metallicity throughout the HVC. However, all of the
Complex C sight lines require significant nitrogen underabundances. Finally, we
compare the 3C 351 sight line to the sight line to the nearby QSO H1821+643 to
search for evidence of outflowing Galactic fountain gas that could be mixing
with Complex C. We find that the intermediate-velocity gas detected toward 3C
351 and H1821+643 has a higher metallicity and may well be a fountain/chimney
outflow from the Perseus spiral arm.Comment: Submitted to AJ. Figures 1-4 compressed for astro-ph; better quality
figures are available at
http://astro.princeton.edu/~tripp/astro/qualitypreps/complexc.ps.g
Versatile Coordination of Cyclopentadienyl-Arene Ligands and Its Role in Titanium-Catalyzed Ethylene Trimerization
Cationic titanium(IV) complexes with ansa-(η5-cyclopentadienyl,η6-arene) ligands were synthesized and characterized by X-ray crystallography. The strength of the metal-arene interaction in these systems was studied by variable-temperature NMR spectroscopy. Complexes with a C1 bridge between the cyclopentadienyl and arene moieties feature hemilabile coordination behavior of the ligand and consequently are active ethylene trimerization catalysts. Reaction of the titanium(IV) dimethyl cations with CO results in conversion to the analogous cationic titanium(II) dicarbonyl species. Metal-to-ligand backdonation in these formally low-valent complexes gives rise to a strongly bonded, partially reduced arene moiety. In contrast to the η6-arene coordination mode observed for titanium, the more electron-rich vanadium(V) cations [cyclopentadienyl-arene]V(NiPr2)(NC6H4-4-Me)+ feature η1-arene binding, as determined by a crystallographic study. The three different metal-arene coordination modes that we experimentally observed model intermediates in the cycle for titanium-catalyzed ethylene trimerization. The nature of the metal-arene interaction in these systems was studied by DFT calculations.
Was ist "PopulĂ€re Musik"? : Ăberlegungen in eigener Sache
Many common disorders across the lifespan feature impaired working memory (WM). Reported benefits of a WM training program include improving inattention in daily life, but this has not been evaluated in a meta-analysis. This study aimed to evaluate whether one WM training method has benefits for inattention in daily life by conducting a systematic review and meta-analysis.We searched Medline and PsycINFO, relevant journals and contacted authors for studies with an intervention and control group reporting post-training estimates of inattention in daily life. To reduce the influence of different WM training methods on the findings, the review was restricted to trials evaluating the Cogmed method. A meta-analysis calculated the pooled standardised difference in means (SMD) between intervention and control groups.A total of 622 studies were identified and 12 studies with 13 group comparisons met inclusion criteria. The meta-analysis showed a significant training effect on inattention in daily life, SMD=-0.47, 95% CI -0.65, -0.29, p<.00001. Subgroup analyses showed this significant effect was observed in groups of children and adults as well as users with and without ADHD, and in studies using control groups that were active and non-adaptive, wait-list and passive as well as studies using specific or general measures. Seven of the studies reported follow-up assessment and a meta-analysis showed persisting training benefits for inattention in daily life, SMD=-0.33, 95% CI -0.57 -0.09, p=.006. Additional meta-analyses confirmed improvements after training on visuospatial WM, SMD=0.66, 95% CI 0.43, 0.89, p<.00001, and verbal WM tasks, SMD=0.40, 95% CI 0.18, 0.62, p=.0004.Benefits of a WM training program generalise to improvements in everyday functioning. Initial evidence shows that the Cogmed method has significant benefits for inattention in daily life with a clinically relevant effect size
A Unified Approach for Process-Based Hydrologic Modeling: 2. Model Implementation and Case Studies
This work advances a unified approach to process-based hydrologic modeling, which we term the âStructure for Unifying Multiple Modeling Alternatives (SUMMA).â The modeling framework, introduced in the companion paper, uses a general set of conservation equations with flexibility in the choice of process parameterizations (closure relationships) and spatial architecture. This second paper specifies the model equations and their spatial approximations, describes the hydrologic and biophysical process parameterizations currently supported within the framework, and illustrates how the framework can be used in conjunction with multivariate observations to identify model improvements and future research and data needs. The case studies illustrate the use of SUMMA to select among competing modeling approaches based on both observed data and theoretical considerations. Specific examples of preferable modeling approaches include the use of physiological methods to estimate stomatal resistance, careful specification of the shape of the within-canopy and below-canopy wind profile, explicitly accounting for dust concentrations within the snowpack, and explicitly representing distributed lateral flow processes. Results also demonstrate that changes in parameter values can make as much or more difference to the model predictions than changes in the process representation. This emphasizes that improvements in model fidelity require a sagacious choice of both process parameterizations and model parameters. In conclusion, we envisage that SUMMA can facilitate ongoing model development efforts, the diagnosis and correction of model structural errors, and improved characterization of model uncertainty
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