687 research outputs found
Molecular Dynamics in Hydrogenâbonded Interactions: A Preliminary Experimentally Determined Harmonic Stretching Force Field for HCNâââHF
Observation of the 2Îœ1 overtone band in the hydrogenâbonded complex HCNâââHF permits evaluation of the anharmonicity constant X 1 1=â116.9(1) cmâ 1 and determination of the anharmonicity corrected fundamental frequency Ï1. This information, and available data from previous rovibrational analyses in the common and perdeuterated isotopic species of HCNâââHF, offer an opportunity for calculation of an approximate stretching harmonic force field. With the assumptions f 1 2=f 2 4=0.0, the remaining force constants (in mdyn/Ă
) are evaluated as: f 1 1=8.600(20), f 2 2=6.228(9), f 3 3=19.115(40), f 4 4=0.2413(39), f 1 3=0.000(13), f 1 4=0.0343(2), f 2 3=â0.211(6), f 3 4=0.000(2). These compare to f 1 1=9.658(2) in the HF monomer and f 1 1=6.244(3) and f 3 3=18.707(16) in the HCN monomer. These results provide the information necessary to quantitatively assess the applicability of the Cummings and Wood approximation in this hydrogenâbonded complex and also give an estimate of D e j , the equilibrium distortion constant in the harmonic limit. Comparisons of these experimentally determined parameters with the predictions of a b i n i t i o molecular orbital calculations at several levels of approximation are presented
The Spectroscopy and Molecular Dynamics of the High Frequency Îœ1 6 Intermolecular Vibrations in HCNâââHF and DCNâââDF
Gas phase rovibrational analysis of the high frequency intermolecular hydrogen bonded bending overtone 2Îœ0 6 [Îœ0=1132.4783(2) cmâ 1] in HCNâââHF and its corresponding perdeuterated fundamental Îœ1 6 [Îœ0=409.1660(2) cmâ 1] are reported. Evaluated rovibrational parameters provide the basis for quantitative modeling of the molecular dynamics associated with this vibration. A quantum mechanical calculation permits determination of the quadratic and quartic force constants K 6 6=537(17) and K 6 6 6 6=4.98(12) cmâ 1 which in turn are used to estimate the pertinent cubic band stretching interaction constants K 4 6 6=â149.3(50) cmâ 1 and account for the unexpected behavior in the rotational constantB 1 6. Second order expansion of the vibrational term energies, give X 4 6=â21.61(2), X 6 7=â7.694(1), X 6 6=â14.84(90), g 6 6=â31.04(90) cmâ 1, neglecting corrections for Fermi resonance. The common isotopic species equilibrium rotational constantB e is evaluated to be 3681.1(11) MHz
Determination of Dissociation Energies and Thermal Functions of Hydrogenâbond Formation using High Resolution FTIR Spectroscopy
A technique which employs high resolution Fourier transform infrared spectroscopy is demonstrated for evaluation of hydrogen bonddissociation energiesD 0 and D e . Results for HCNââHF give a D 0=20.77(22) and D e =28.77(45) kJ/mol which are compared with previously determined values obtained from microwave absolute intensity measurements and a b i n i t i o molecular orbital calculations. Rovibrational band information available for HCNââHF also permits evaluation of thermal functions of dimer formation in kJ/mol: ÎU â 298.2 =20.1(2), ÎH â 298.2 =22.6(2), ÎG â 298.2 =59.4(2), ÎS â 298.2 =â0.1235
LEGUS and Halpha-LEGUS Observations of Star Clusters in NGC 4449: Improved Ages and the Fraction of Light in Clusters as a Function of Age
We present a new catalog and results for the cluster system of the starburst
galaxy NGC 4449 based on multi-band imaging observations taken as part of the
LEGUS and Halpha-LEGUS surveys. We improve the spectral energy fitting method
used to estimate cluster ages and find that the results, particularly for older
clusters, are in better agreement with those from spectroscopy. The inclusion
of Halpha measurements, the role of stochasticity for low mass clusters, the
assumptions about reddening, and the choices of SSP model and metallicity all
have important impacts on the age-dating of clusters. A comparison with ages
derived from stellar color-magnitude diagrams for partially resolved clusters
shows reasonable agreement, but large scatter in some cases. The fraction of
light found in clusters relative to the total light (i.e., T_L) in the U, B,
and V filters in 25 different ~kpc-size regions throughout NGC 4449 correlates
with both the specific Region Luminosity, R_L, and the dominant age of the
underlying stellar population in each region. The observed cluster age
distribution is found to decline over time as dN/dt ~ t^g, with g=-0.85+/-0.15,
independent of cluster mass, and is consistent with strong, early cluster
disruption. The mass functions of the clusters can be described by a power law
with dN/dM ~ M^b and b=-1.86+/-0.2, independent of cluster age. The mass and
age distributions are quite resilient to differences in age-dating methods.
There is tentative evidence for a factor of 2-3 enhancement in both the star
and cluster formation rate ~100 - 300 Myr ago, indicating that cluster
formation tracks star formation generally. The enhancement is probably
associated with an earlier interaction event
Sampling Local Fungal Diversity in an Undergraduate Laboratory using DNA Barcoding
Traditional methods for fungal species identification require diagnostic morphological characters and are often limited by the availability of fresh fruiting bodies and local identification resources. DNA barcoding offers an additional method of species identification and is rapidly developing as a critical tool in fungal taxonomy. As an exercise in an undergraduate biology course, we identified 9 specimens collected from the Hendrix College campus in Conway, Arkansas, USA to the genus or species level using morphology. We report that DNA barcoding targeting the internal transcribed spacer (ITS) region supported several of our taxonomic determinations and we were able to contribute 5 ITS sequences to GenBank that were supported by vouchered collection information. We suggest that small-scale barcoding projects are possible and that they have value for documenting fungal diversity
Pyrophosphate-Dependent ATP Formation from Acetyl Coenzyme A in Syntrophus aciditrophicus, a New Twist on ATP Formation.
UnlabelledSyntrophus aciditrophicus is a model syntrophic bacterium that degrades key intermediates in anaerobic decomposition, such as benzoate, cyclohexane-1-carboxylate, and certain fatty acids, to acetate when grown with hydrogen-/formate-consuming microorganisms. ATP formation coupled to acetate production is the main source for energy conservation by S. aciditrophicus However, the absence of homologs for phosphate acetyltransferase and acetate kinase in the genome of S. aciditrophicus leaves it unclear as to how ATP is formed, as most fermentative bacteria rely on these two enzymes to synthesize ATP from acetyl coenzyme A (CoA) and phosphate. Here, we combine transcriptomic, proteomic, metabolite, and enzymatic approaches to show that S. aciditrophicus uses AMP-forming, acetyl-CoA synthetase (Acs1) for ATP synthesis from acetyl-CoA. acs1 mRNA and Acs1 were abundant in transcriptomes and proteomes, respectively, of S. aciditrophicus grown in pure culture and coculture. Cell extracts of S. aciditrophicus had low or undetectable acetate kinase and phosphate acetyltransferase activities but had high acetyl-CoA synthetase activity under all growth conditions tested. Both Acs1 purified from S. aciditrophicus and recombinantly produced Acs1 catalyzed ATP and acetate formation from acetyl-CoA, AMP, and pyrophosphate. High pyrophosphate levels and a high AMP-to-ATP ratio (5.9 ± 1.4) in S. aciditrophicus cells support the operation of Acs1 in the acetate-forming direction. Thus, S. aciditrophicus has a unique approach to conserve energy involving pyrophosphate, AMP, acetyl-CoA, and an AMP-forming, acetyl-CoA synthetase.ImportanceBacteria use two enzymes, phosphate acetyltransferase and acetate kinase, to make ATP from acetyl-CoA, while acetate-forming archaea use a single enzyme, an ADP-forming, acetyl-CoA synthetase, to synthesize ATP and acetate from acetyl-CoA. Syntrophus aciditrophicus apparently relies on a different approach to conserve energy during acetyl-CoA metabolism, as its genome does not have homologs to the genes for phosphate acetyltransferase and acetate kinase. Here, we show that S. aciditrophicus uses an alternative approach, an AMP-forming, acetyl-CoA synthetase, to make ATP from acetyl-CoA. AMP-forming, acetyl-CoA synthetases were previously thought to function only in the activation of acetate to acetyl-CoA
Using H-alpha Morphology and Surface Brightness Fluctuations to Age-Date Star Clusters in M83
We use new WFC3 observations of the nearby grand design spiral galaxy M83 to
develop two independent methods for estimating the ages of young star clusters.
The first method uses the physical extent and morphology of Halpha emission to
estimate the ages of clusters younger than tau ~10 Myr. It is based on the
simple premise that the gas in very young (tau < few Myr) clusters is largely
coincident with the cluster stars, is in a small, ring-like structure
surrounding the stars in slightly older clusters (e.g., tau ~5 Myr), and is in
a larger ring-like bubble for still older clusters (i.e., ~5-10 Myr). The
second method is based on an observed relation between pixel-to-pixel flux
variations within clusters and their ages. This method relies on the fact that
the brightest individual stars in a cluster are most prominent at ages around
10 Myr, and fall below the detection limit (i.e., M_V < -3.5) for ages older
than about 100 Myr. These two methods are the basis for a new morphological
classification system which can be used to estimate the ages of star clusters
based on their appearance. We compare previous age estimates of clusters in M83
determined from fitting UBVI Halpha measurements using predictions from stellar
evolutionary models with our new morphological categories and find good
agreement at the ~95% level. The scatter within categories is ~0.1 dex in log
tau for young clusters (10 Myr) clusters. A
by-product of this study is the identification of 22 "single-star" HII regions
in M83, with central stars having ages ~4 Myr.Comment: 33 pages, 10 figures, 3 tables; published in March Ap
High Fat Relative to Low Fat Ground Beef Consumption Lowers Blood Pressure and Does Not Negatively Alter Arterial Stiffness
Beef consumption has been stigmatized as an unhealthy dietary choice. However, randomized control trials to support this claim are lacking. PURPOSE: To examine the effect of low-fat (5%) and high-fat (25%) ground beef consumption on blood pressure (BP) and carotid-femoral pulse wave velocity (PWV).METHODS: Twenty-three male subjects (age 40±11 yrs, height 177.4±6.7 cm, weight 97.3±25.0 kg, lean mass 64.5±9.5 kg, fat mass 30.6±19.1 kg) volunteered to participate in this cross-over design study. Each participant completed two, 5-week ground beef interventions in a randomized order with a 4-week washout period in-between. All participants visited the lab four times after an overnight fast. Each visit to the lab consisted of supine BP, dual energy x-ray absorptiometry (DXA) scan to assess body composition, and PWV analysis. The PWV recording was assessed on the right carotid and femoral arteries. The distance used for the PWV calculation was 80% of the actual distance between carotid and femoral sites. All PWV measures were completed according to previously published procedures (Van Bortel, 2011). BP and PWV results were analyzed separately via 2x2 repeated measures ANOVA. RESULTS: Our results indicate there was a significant decrease in systolic BP (p=0.01) following the high-fat ground beef intervention compared to the low-fat. The BP values for low-fat beef and high-fat beef are 120/74 and 116/73 mmHg, respectively. Further, there were no significant differences between the PWV measures. CONCLUSION: Based on our results, high fat ground beef favorably alters systolic BP and does not negatively affect PWV measures
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