Density functional theory study on the activation of molecular oxygen on a stepped gold surface in an aqueous environment: a new approach for simulating reactions in solution

The activation of oxygen molecules is an important issue in the gold-catalyzed partial oxidation of alcohols in aqueous solution. The complexity of the solution arising from a large number of solvent molecules makes it difficult to study the reaction in the system. In this work, O-2 activation on an Au catalyst is investigated using an effective approach to estimate the reaction barriers in the presence of solvent. Our calculations show that O-2 can be activated, undergoing OOH* in the presence of water molecules. The OOH* can readily be formed on Au(211) via four possible pathways with almost equivalent free energy barriers at the aqueous-solid interface: the direct or indirect activation of O-2 by surface hydrogen or the hydrolysis of O-2 following a Langmuir-Hinshelwood mechanism or an Eley-Rideal mechanism. Among them, the Eley-Rideal mechanism may be slightly more favorable due to the restriction of the low coverage of surface H on Au(211) in the other mechanisms. The results shed light on the importance of water molecules on the activation of oxygen in gold-catalyzed systems. Solvent is found to facilitate the oxygen activation process mainly by offering extra electrons and stabilizing the transition states. A correlation between the energy barrier and the negative charge of the reaction center is found. The activation barrier is substantially reduced by the aqueous environment, in which the first solvation shell plays the most important role in the barrier reduction. Our approach may be useful for estimating the reaction barriers in aqueous systems.

Ultralow-temperature CO oxidation on an In2O3-Co3O4 catalyst: a strategy to tune CO adsorption strength and oxygen activation simultaneously

Highly efficient In2O3-Co3O4 catalysts were prepared for ultralow-temperature CO oxidation by simultaneously tuning the CO adsorption strength and oxygen activation over a Co3O4 surface, which could completely convert CO to CO2 at temperatures as low as -105 degrees C compared to -40 degrees C over pure Co3O4, with enhanced stability.

Evidence To Challenge the Universality of the Horiuti-Polanyi Mechanism for Hydrogenation in Heterogeneous Catalysis:Origin and Trend of the Preference of a Non-Horiuti-Polanyi Mechanism

The Horiuti-Polanyi mechanism has been considered to be universal for explaining the mechanisms of hydrogenation reactions in heterogeneous catalysis for several decades. In this work, we examine this mechanism for the hydrogenation of acrolein, the simplest alpha,beta-unsaturated aldehyde, in gold-based systems as well as some other metals using extensive first-principles calculations. It is found that a non-Horiuti-Polanyi mechanism is favored in some cases. Furthermore, the physical origin and trend of this mechanism are revealed and discussed regarding the geometrical and electronic effects, which will have a significant influence on current understandings on heterogeneous catalytic hydrogenation reactions and the future catalyst design for these reactions.

A density functional theory study of hydrogen dissociation and diffusion at the perimeter sites of Au/TiO2

Reactivity of supported gold catalysts is a hot topic in catalysis for many years. This communication reports an investigation on the dissociation of molecular hydrogen at the perimeter sites of Au/TiO2 and the spillover of hydrogen atoms from the gold to the support using density functional theory calculations. It is found that the heterolytic dissociation is favoured in comparison with homolytic dissociation of molecular hydrogen at the perimeter sites. However, the surface oxygen of the rutile TiO2(110) surface at these sites can be readily passivated by the formed OH, suggesting that further dissociation of molecular hydrogen may occur at pure gold sites.

Combining multi-band and frequency-filtering techniques for speech recognition in noisy environments

While current speech recognisers give acceptable performance in carefully controlled environments, their performance degrades rapidly when they are applied in more realistic situations. Generally, the environmental noise may be classified into two classes: the wide-band noise and narrow band noise. While the multi-band model has been shown to be capable of dealing with speech corrupted by narrow-band noise, it is ineffective for wide-band noise. In this paper, we suggest a combination of the frequency-filtering technique with the probabilistic union model in the multi-band approach. The new system has been tested on the TIDIGITS database, corrupted by white noise, noise collected from a railway station, and narrow-band noise, respectively. The results have shown that this approach is capable of dealing with noise of narrow-band or wide-band characteristics, assuming no knowledge about the noisy environment.

In Situ Gelling Ophthalmic Drug Delivery System: An Overview and Its Applications.

Ophthalmic drug delivery system is very interesting and challenging due to the normal physiologically factor of eyes which reduces the bioavailability of ocular products. The development of a new ophthalmic dosage forms with the existing drugs to improve efficacy and bioavailability including better patients' compliance and convenience has become trend in the most pharmaceutical industries. The present review encompasses various conventional and novel ocular drug delivery systems, methods of preparation, characterization, recent researches carried out. Furthermore, the information on various commercially available in situ gel preparations and the existing patents of in situ drug delivery systems i.e. in situ gel formation of pectin, in situ gel for therapeutic use, medical uses of in situ formed gels and in situ gelling systems as sustained delivery for front of eye also covered in this review.

Robust bimodal person identification using face and speech with limited training data and corruption of both modalities

This paper presents a novel method of audio-visual fusion for person identification where both the speech and facial modalities may be corrupted, and there is a lack of prior knowledge about the corruption. Furthermore, we assume there is a limited amount of training data for each modality (e.g., a short training speech segment and a single training facial image for each person). A new representation and a modified cosine similarity are introduced for combining and comparing bimodal features with limited training data as well as vastly differing data rates and feature sizes. Optimal feature selection and multicondition training are used to reduce the mismatch between training and testing, thereby making the system robust to unknown bimodal corruption. Experiments have been carried out on a bimodal data set created from the SPIDRE and AR databases with variable noise corruption of speech and occlusion in the face images. The new method has demonstrated improved recognition accuracy.

An iterative longest matching segment approach to speech enhancement with additive noise and channel distortion

This paper presents a new approach to speech enhancement from single-channel measurements involving both noise and channel distortion (i.e., convolutional noise), and demonstrates its applications for robust speech recognition and for improving noisy speech quality. The approach is based on finding longest matching segments (LMS) from a corpus of clean, wideband speech. The approach adds three novel developments to our previous LMS research. First, we address the problem of channel distortion as well as additive noise. Second, we present an improved method for modeling noise for speech estimation. Third, we present an iterative algorithm which updates the noise and channel estimates of the corpus data model. In experiments using speech recognition as a test with the Aurora 4 database, the use of our enhancement approach as a preprocessor for feature extraction significantly improved the performance of a baseline recognition system. In another comparison against conventional enhancement algorithms, both the PESQ and the segmental SNR ratings of the LMS algorithm were superior to the other methods for noisy speech enhancement.

Speech Enhancement from Additive Noise and Channel Distortion - a Corpus-Based Approach

This paper presents a new approach to single-channel speech enhancement involving both noise and channel distortion (i.e., convolutional noise). The approach is based on finding longest matching segments (LMS) from a corpus of clean, wideband speech. The approach adds three novel developments to our previous LMS research. First, we address the problem of channel distortion as well as additive noise. Second, we present an improved method for modeling noise. Third, we present an iterative algorithm for improved speech estimates. In experiments using speech recognition as a test with the Aurora 4 database, the use of our enhancement approach as a preprocessor for feature extraction significantly improved the performance of a baseline recognition system. In another comparison against conventional enhancement algorithms, both the PESQ and the segmental SNR ratings of the LMS algorithm were superior to the other methods for noisy speech enhancement. Index Terms: corpus-based speech model, longest matching segment, speech enhancement, speech recognition

A technique for reducing strain concentrations in FRP wrapped concrete columns

Existing studies have shown conclusively that the measured fibre reinforced polymer (FRP) rupture strain in FRP wrapped concrete columns is usually significantly smaller than the rupture strain obtained from flat coupon tests. One of the main causes for this phenomenon is the existence of geometrical discontinuities at both ends of the FRP sheets. This study proposes a new strengthening method in which continuous FRP spiral wrapping is used to eliminate strain concentrations due to the geometrical discontinuities and thus increase the FRP rupture strain at column failure. The effect of the spiral angle of FRP on the FRP rupture strain in FRP wrapped specimens was experimentally investigated. The test results indicate that the spiral wrapping with a small angle with respect to the column circumference can significantly increase the strain efficiency of FRP and thus enhance the axial compression capacity of the strengthened cylinders.

Economical and coordinated dispatch of CHP based microgrid with renewable energy resources

The advantages of high energy efficiency and economic benefit promote the wide application of combined heat and power system (CHP) based microgrid. Firstly, a mathematical model of the CHP based microgrid is developed. Then, a cost function for the coordination of heat and electric load is proposed. Finally, an optimal dispatch model is developed to achieve the economical and coordinated operation of the CHP based microgrid system. Simulation results verify effectiveness of the proposed dispatch model, which is a powerful tool for the energy management of CHP based microgrid with renewable energy resources.

Combining Bio- and Chemo-Catalysis for the Conversion of Bio-Renewable Alcohols: Homogeneous Iridium Catalysed Hydrogen Transfer Initiated Dehydration of 1,3-Propanediol to Aldehydes

Combining whole cell biocatalysis and chemocatalysis in a single reaction sequence avoids unnecessary separations, and the associated waste and energy consumption. Bacterial fermentation has been employed to convert waste glycerol from biodiesel production into 1,3-propanediol. This 1,3-propanediol can be extracted selectively from the aqueous fermentation broth using ionic liquids. 1,3-propanediol in ionic liquid solution was converted to propanal by hydrogen transfer initiated dehydration (HTID) catalysed by a Cp*IrCl2(NHC) (Cp* = pentamethylcyclopentadienyl; NHC = carbene ligand) complex. The use of an ionic liquid solvent enabled the reaction to be performed under reduced pressure, facilitating the isolation of the product, and improving the reaction selectivity. The Ir(III) catalyst in ionic liquid was found to be highly recyclable.

PRL-3 activates mTORC1 in Cancer Progression

PRL-3, a metastasis-associated phosphatase, is known to exert its oncogenic functions through activation of PI3K/Akt, which is a key regulator of the rapamycin-sensitive mTOR complex 1 (mTORC1), but a coherent link between PRL-3 and activation of mTOR has not yet been formally demonstrated. We report a positive correlation between PRL-3 expression and mTOR phospho-activation in clinical tumour samples and mouse models of cancer and demonstrate that PRL-3 increased downstream signalling to the mTOR substrates, p70S6K and 4E-BP1, by increasing PI3K/Akt-mediated activation of Rheb-GTP via TSC2 suppression. We also show that PRL-3 increases mTOR translocation to lysosomes via increased mTOR binding affinity to Rag GTPases in an Akt-independent manner, demonstrating a previously undescribed mechanism of action for PRL-3. PRL-3 also enhanced matrix metalloproteinase-2 secretion and cellular invasiveness via activation of mTOR, attributes which were sensitive to rapamycin treatment. The downstream effects of PRL-3 were maintained even under conditions of environmental stress, suggesting that PRL-3 provides a strategic survival advantage to tumour cells via its effects on mTOR.