Chloroform Hydrodechlorination on Palladium Surfaces: A Comparative DFT Study on Pd(111), Pd(100), and Pd(211)

Topics in Catalysis - Palladium has been shown to be an effective catalyst for chloroform hydrodechlorination, which serves as a promising treatment method for industrial chloroform waste. To...     

Determinants of genital human papillomavirus infection among cytologically normal women attending the University of New Mexico student health center

OBJECTIVES: To confirm the risk factors for genital human papillomavirus (HPV) infection. GOAL OF THIS STUDY: To investigate risk factors for HPV detection apart from the correlated risk factors for cervical neoplasia. STUDY DESIGN: Cervical human papillomavirus (HPV) DNA was assessed in 357 cytologically normal women attending the University of New Mexico student health center. Cervical swab samples were obtained for HPV DNA detection and typing using a PCR-based DNA amplification system. Possible determinants of cervical HPV were examined including age, ethnicity, history of sexually transmitted disease, oral contraceptive use, smoking, age at first intercourse, lifetime number of sex partners, marital status, and history of pregnancy. RESULTS: A 44.3% overall prevalence of cervical HPV was observed. On univariate analysis, factors associated with increasing HPV prevalence included higher lifetime number of sex partners and single marital status. After adjustment for potential confounding variables, we found that HPV prevalence increased with higher lifetime number of sexual partners. CONCLUSION: These findings, along with those from the companion reports in this issue of the journal, support the sexual route of transmission of the virus.     

Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT) calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910]. Results from reaction kinetics experiments show that the rate of H₂ production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by the presence of CO or H₂ with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH₃OH→H₂COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species.     

Microblog language identification: overcoming the limitations of short, unedited and idiomatic text

Multilingual posts can potentially affect the outcomes of content analysis on microblog platforms. To this end, language identification can provide a monolingual set of content for analysis. We find the unedited and idiomatic language of microblogs to be challenging for state-of-the-art language identification methods. To account for this, we identify five microblog characteristics that can help in language identification: the language profile of the blogger (blogger), the content of an attached hyperlink (link), the language profile of other users mentioned (mention) in the post, the language profile of a tag (tag), and the language of the original post (conversation), if the post we examine is a reply. Further, we present methods that combine these priors in a post-dependent and post-independent way. We present test results on 1,000 posts from five languages (Dutch, English, French, German, and Spanish), which show that our priors improve accuracy by 5 % over a domain specific baseline, and show that post-dependent combination of the priors achieves the best performance. When suitable training data does not exist, our methods still outperform a domain unspecific baseline. We conclude with an examination of the language distribution of a million tweets, along with temporal analysis, the usage of twitter features across languages, and a correlation study between classifications made and geo-location and language metadata fields.     

Scanning tunnelling microscopy of tobacco mosaic virus on evaporated and sputter-coated palladium/gold substrates

We present scanning tunnelling microscope (STM) images of untreated tobacco mosaic virus (TMV) deposited on thermally evaporated and on sputter-coated palladium/gold 40:60 (Pd/Au) substrates, and imaged under ordinary atmospheric conditions. The TMV imaged on both evaporated and sputter-coated substrates was consistently several times wider than the known diameter of the virus. TMV on evaporated Pd/Au became overcoated with Pd/Au material during sample preparation and appeared elevated in STM images, whereas TMV on sputter-coated Pd/Au appeared as depressions. When naked TMV were intentionally overcoated with Pd/Au, the STM images were found to be similar to those for TMV on evaporated Pd/Au.     

Formic acid decomposition on Au catalysts: DFT,microkinetic modeling,and reaction kinetics experiments

A combined theoretical and experimental approach is presented that uses a comprehensive mean‐field microkinetic model, reaction kinetics experiments, and scanning transmission electron microscopy imaging to unravel the reaction mechanism and provide insights into the nature of active sites for formic acid (HCOOH) decomposition on Au/SiC catalysts. All input parameters for the microkinetic model are derived from periodic, self‐consistent, generalized gradient approximation (GGA‐PW91) density functional theory calculations on the Au(111), Au(100), and Au(211) surfaces and are subsequently adjusted to describe the experimental HCOOH decomposition rate and selectivity data. It is shown that the HCOOH decomposition follows the formate (HCOO) mediated path, with 100% selectivity toward the dehydrogenation products (CO₂ + H₂) under all reaction conditions. An analysis of the kinetic parameters suggests that an Au surface in which the coordination number of surface Au atoms is ≤4 may provide a better model for the active site of HCOOH decomposition on these specific supported Au catalysts. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1303–1319, 2014     

Transesterification of rapeseed oil for the production of biodiesel using homogeneous and heterogeneous catalysis

In the present work, the transesterification reaction of rapeseed oil with methanol, in the presence of alkaline catalysts, either homogeneous (NaOH) or heterogeneous (Mg MCM-41, Mg–Al Hydrotalcite, and K+ impregnated zirconia), using low frequency ultrasonication (24 kHz) and mechanical stirring (600 rpm) for the production of biodiesel fuel was studied. Selection of heterogeneous catalysts was based on a combination of their porosity and surface basicity. Their characterization was carried out using X-ray diffraction (XRD), Nitrogen adsorption–desorption porosimetry and scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS). The activities of the catalysts were related to their basic strength. Mg–Al hydrotalcite showed particularly the highest activity with conversion reaching 97%). The activity of ZrO₂ in the transesterification reaction increased as the catalyst was doped with more potassium cations, becoming thus more basic. Use of ultrasonication significantly accelerated the transesterification reaction compared to the use of mechanical stirring (5 h vs. 24 h).Given the differences in experimental design, it can be concluded that the homogeneous catalyst accelerated significantly the transesterification reaction, as compared to all heterogeneous catalysts, using both mechanical stirring (15 min vs. 24 h) and ultrasonication (10 min vs. 5 h). However, the use of homogeneous base catalysts requires neutralization and separation from the reaction mixture leading to a series of environmental problems related to the use of high amounts of solvents and energy. Heterogeneous solid base catalysts can be easily separated from the reaction mixture by simple filtration, they are easily regenerated and bear a less corrosive nature, leading to safer, cheaper and more environment-friendly operations.     

A novel wideband and circularly polarized cross‐dipole antenna

In this paper, we present a novel wideband circularly polarized (CP) composite, called cavity‐backed crossed dipole antenna for 2.45 GHz industrial, scientific, and medical (ISM) band wireless communication. To excite the CP radiation effectively, a curved‐delay line providing an orthogonal phase difference among the cross‐dipole elements is attached at corners of the sequentially rotated elements. By choosing a proper radius of the curved‐delay line, a wide input impedance of the antenna can be realized. Unlike conventional cross‐dipole antennas, the proposed cross‐dipole antenna is designed with an open stub added to the radiating arms of the dipole so that both impedance and axial ratio bandwidths are enhanced. The antenna is center‐fed by a 50‐Ω coaxial cable and is placed above a cavity‐backed reflector to obtain a directional CP radiation pattern. With the advantage of being center‐fed, a symmetric CP radiation pattern can be achieved across the entire operating bandwidth. To further improve the directivity and the radiation pattern, a rectangular cavity‐backed reflector is used. Simulated and measured results confirm that the proposed antenna has good CP characteristics. The proposed antenna obtains a broad 3‐dB axial ratio bandwidth of 49% (1.20 GHz, 1.96–3.16 GHz) and an impedance bandwidth of 67.7% (1.66 GHz, 1.69–3.35 GHz) for reflection coefficient (S₁₁) ≦ −10 dB. It also yields an average CP gain of 9.2 dBic across the operating bandwidth and a peak CP gain of 10 dBic. Copyright © 2016 John Wiley & Sons, Ltd.     

Inhibition Studies of Mycobacterium tuberculosis Salicylate Synthase (MbtI)

Mycobacterium tuberculosis salicylate synthase (MbtI), a member of the chorismate‐utilizing enzyme family, catalyses the first committed step in the biosynthesis of the siderophore mycobactin T. This complex secondary metabolite is essential for both virulence and survival of M. tuberculosis, the etiological agent of tuberculosis (TB). It is therefore anticipated that inhibitors of this enzyme may serve as TB therapies with a novel mode of action. Herein we describe the first inhibition study of M. tuberculosis MbtI using a library of functionalized benzoate‐based inhibitors designed to mimic the substrate (chorismate) and intermediate (isochorismate) of the MbtI‐catalyzed reaction. The most potent inhibitors prepared were those designed to mimic the enzyme intermediate, isochorismate. These compounds, based on a 2,3‐dihydroxybenzoate scaffold, proved to be low‐micromolar inhibitors of MbtI. The most potent inhibitors in this series possessed hydrophobic enol ether side chains at C3 in place of the enol‐pyruvyl side chain found in chorismate and isochorismate.     

Discrete chiasma formation models and their associated high order interference

We introduce some special chiasma formation processes. First a family of discrete chiasma formation processes is introduced and we determine the nature of higher order interference associated with those processes. Secondly we consider a two-stage chiasma formation process, where the associated recombination frequency between two markers depends not only on their map distance but also on their location along the chromosomes. We characterise under this process, in some cases, the nature of interference between two segments.