Kinetics of homogeneous catalytic chlorination of acetic acid

The kinetics of the chlorination of acetic acid (HAc) to monochloroacetic acid (MCA) and the physical solubility of chlorine in HAc and its mixtures with MCA were investigated in a laboratory scale semibatch reactor. The temperature dependence of the Henry's constant was determined from solubility data obtained at temperatures between 70°C and 110°C. The kinetic experiments were performed at 75–100°C with 3–13 mol % acetyl chloride (AcCl) and 0–5 weight % H₂SO₄ added as catalysts. Gas chromatography was used to determine the concentrations of HAc, MCA, dichloroacetic acid and AcCl during the experiments. The results indicate that the reaction rate is independent of the concentrations of HAc and Cl₂ whereas the reaction is significantly enhanced by MCA and H₂SO₄. The effects are explained by a reaction mechanism involving the acid catalyzed enolization of AcCl as the rate-determining step. A rate equation based on this mechanism was derived. Kinetic constants included in the equation were determined by regression analysis.     

Recovering selenium from copper refinery slimes

The selenium contained within copper refinery slimes may be recovered advantageously by roasting at about 600°C. While roasting in air is inefficient, roasting in a sulfating atmosphere enables practically complete selenium recovery. Based on laboratory tests, a new selenium recovery process was adopted at Outokumpu Copper Refinery. In this process, sulfation is achieved by feeding sulfur dioxide and oxygen into the roasting furnace.     

iRGD-Liposomes Enhance Tumor Delivery and Therapeutic Efficacy of Antisense Oligonucleotide Drugs against Primary Prostate Cancer and Bone Metastasis

Nucleotide-based drugs, such as antisense oligonucleotides (ASOs), have unique advantages in treating human diseases as they provide virtually unlimited ability to target any gene. However, their clinical translation faces many challenges, one of which is poor delivery to the target tissue in vivo. This problem is particularly evident in solid tumors. Here, liposomes are functionalized with a tumor-homing and -penetrating peptide, iRGD, as a carrier of an ASO against androgen receptor (AR) for prostate cancer treatment. The iRGD-liposomes exhibit a high loading efficiency of AR-ASO, and an efficient knockdown of AR gene products is achieved in vitro, including AR splice variants. In vivo, iRGD-liposomes significantly increase AR-ASO accumulation in the tumor tissue and decrease AR expression relative to free ASOs in prostate tumors established as subcutaneous xenografts. Similar results are obtained with intra-tibial xenografts modeling metastasis to bones, the predominant site of metastasis for prostate cancer. In treatment studies, iRGD-liposomes markedly improve the AR-ASO efficacy in suppressing the growth of both subcutaneous xenografts and intra-tibial xenografts. The inhibitory effect on tumor growth is also significantly prolonged by the delivery of the AR-ASO in the iRGD-liposomes. Meanwhile, iRGD-liposomes does not increase ASO accumulation or toxicity in healthy organs. Overall, a delivery system that can significantly increase ASO accumulation and efficacy in solid tumors is provided here. These benefits are achieved without significant side effects, providing a way to increase the antitumor efficacy of ASOs.     

GPU-accelerated and parallelized ELM ensembles for large-scale regression

The paper presents an approach for performing regression on large data sets in reasonable time, using an ensemble of extreme learning machines (ELMs). The main purpose and contribution of this paper are to explore how the evaluation of this ensemble of ELMs can be accelerated in three distinct ways: (1) training and model structure selection of the individual ELMs are accelerated by performing these steps on the graphics processing unit (GPU), instead of the processor (CPU); (2) the training of ELM is performed in such a way that computed results can be reused in the model structure selection, making training plus model structure selection more efficient; (3) the modularity of the ensemble model is exploited and the process of model training and model structure selection is parallelized across multiple GPU and CPU cores, such that multiple models can be built at the same time. The experiments show that competitive performance is obtained on the regression tasks, and that the GPU-accelerated and parallelized ELM ensemble achieves attractive speedups over using a single CPU. Furthermore, the proposed approach is not limited to a specific type of ELM and can be employed for a large variety of ELMs.     

Effect of 2-propanol and water contents on the crystallization and particle size of titanium dioxide synthesized at low-temperature

Two series of titanium dioxide, TiO₂, powder were prepared at a temperature of 50 °C without any catalyst. The effects of 2-propanol and water contents on the formation of crystalline powder mixture of anatase and brookite were systematically studied. The characteristics of produced powder were determined by employing X-ray diffraction, transmission electron microscopy, nitrogen adsorption test and Fourier transform infrared spectroscopy.     

Mid‐infrared spectroscopy and multivariate curve resolution for analyzing human adipose tissue triacylglycerols

The aim of this study was to evaluate use of infrared spectroscopy for measuring adipose tissue triacylglycerols (TAGs) with analysis by multivariate curve resolution (MCR). The mid‐infrared spectrum was measured with an attenuated total reflection accessory from a lipid droplet pressed from adipose tissue. The obtained spectra were characteristic of pure TAG spectra and water and protein contamination could be easily identified from specific spectral regions. MCR analysis of the olefinic (?C? H) stretch (3006 cm^?1), resolved the different contributions of monounsaturated (MUFA) and polyunsaturated (PUFA) double bonds. Similar MCR analysis of the trans (HC?CH? ) region (966 cm^?1), resolved the differing contributions of isolated trans isomers (transFA) and CLA. The PUFA double bond content of 16 subjects was negatively correlated with concentrations of serum total cholesterol R = ?0.498 (p = 0.050) and triacylglycerols R = ?0.609, (p = 0.016). The transFA content exhibited a negative, although non‐significant, correlation to high‐density lipoprotein (HDL)‐cholesterol (R = ?0.483, p = 0.068). The present study shows that MCR analysis of adipose tissue TAG infrared spectra can be used to estimate differences in the fatty acid (FA) profiles in population studies. Infrared spectroscopy in combination with MCR provides a robust method for assessing a FA profile of human adipose tissue. Practical applications: This study has highlighted the use of MCR to enhance the information obtained from infrared spectra. This new approach provides a robust method for assessing a FA profile of human adipose tissue lipids.     

Extracellular enzyme activities and nutrient availability during artificial groundwater recharge

Natural organic matter (NOM) removal is the main objective of artificial groundwater recharge (AGR) for drinking water production and biodegradation plays a substantial role in this process. This study focused on the biodegradation of NOM and nutrient availability for microorganisms in AGR by the determination of extracellular enzyme activities (EEAs) and nutrient concentrations along a flow path in an AGR aquifer (Tuusula Water Works, Finland). Natural groundwater in the same area but outside the influence of recharge was used as a reference. Determination of the specific α-d-glucosidase (α-Glu), β-d-glucosidase (β-Glu), phosphomonoesterase (PME), leucine aminopeptidase (LAP) and acetate esterase (AEST) activities by fluorogenic model substrates revealed major increases in the enzymatic hydrolysis rates in the aquifer within a 10 m distance from the basin. The changes in the EEAs along the flow path occurred simultaneously with decreases in nutrient concentrations. The results support the assumption that the synthesis of extracellular enzymes in aquatic environments is up and down regulated by nutrient availability. The EEAs in the basin sediment and pore water samples (down to 10 cm) were in the same order of magnitude as in the basin water, suggesting similar nutritional conditions. Phosphorus was likely to be the limiting nutrient at this particular AGR site. Furthermore, the extracellular enzymes functioned in a synergistic and cooperative way.     

Simultaneous estimation of spatially distributed thermal conductivity,heat capacity and surface heat transfer coefficient in thermal tomography

In thermal tomography, the thermal properties of a target are estimated as spatially distributed parameters based on non-invasive measurements of surface temperatures. In the measurement setup, the target is sequentially heated at different source locations and the induced temperature evolutions are measured at several measurement locations on the surface. In [V. Kolehmainen, J. Kaipio, H. Orlande, Reconstruction of thermal conductivity and heat capacity using a tomographic approach, Int. J. Heat Mass Transfer 50 (25–26) (2007) 5150–5160], it was demonstrated with simulations that simultaneous estimation of spatially distributed thermal conductivity and volumetric heat capacity from transient boundary data is feasible when the boundary heat flux from the target to the surrounding medium is known all over the target boundary. In this article, we extend the computational methods towards the more practical setup of imaging targets, where the boundary heat flux from the target to the surrounding medium is not known. We model the surface heat transfer coefficient as a spatially distributed parameter on the target boundary and estimate it simultaneously with the spatially distributed thermal conductivity and volumetric heat capacity using the statistical (Bayesian) inversion framework. The feasibility of the approach is evaluated with simulations.     

Performance evaluation of a Kademlia-based communication-oriented P2P system under churn

The phenomenon of churn has a significant effect on the performance of Peer-to-Peer (P2P) networks, especially in mobile environments that are characterized by intermittent connections and unguaranteed network bandwidths. A number of proposals have been put forward to deal with this problem; however, we have so far not seen any thorough analysis to guide the optimal design choices and parameter configurations for structured P2P networks. In this article, we present a performance evaluation of a structured communication-oriented P2P system in the presence of churn. The evaluation is conducted using both simulation models and a real-life prototype implementation. In both evaluation environments, we utilize Kademlia with some modifications as the underlying distributed hash table (DHT) algorithm, and Peer-to-Peer Protocol (P2PP) as the signaling protocol. The results from the simulation models created using Nethawk EAST (a telecommunication simulator software) suggest that, in most situations, a lookup parallelism degree of 3 and resource replication degree of 3 are enough for guaranteeing a high resource lookup success ratio. We also notice that, with the parallel lookup mechanism, a good success ratio is achieved even without the KeepAlive traffic that is used for detecting the aliveness of nodes. A prototype system that works in mobile environment is implemented to evaluate the feasibility of mobile nodes acting as full-fledged peers. The measurements made using the prototype show that, from the viewpoints of CPU load and network traffic load, it is feasible for the mobile nodes to take part in the overlay. Through energy consumption measurements, we draw the conclusion that in general the UMTS access mode consumes slightly more power than the WLAN access mode. Protocol packets with sizes of 200 bytes or less are observed to be the most energy efficient in the UMTS access mode.