Efficient allylation of cellulose in dimethyl sulfoxide/tetrabutylammonium fluoride trihydrate

The cellulose solvent dimethyl sulfoxide (DMSO)/tetrabutylammonium fluoride trihydrate (TBAF) was successfully applied as reaction medium for the synthesis of allyl cellulose by conversion of the polymer with allyl chloride in the presence of solid NaOH. Samples with degree of substitution from 0.50 to 2.98 were accessible by varying the molar ratio anhydroglucose unit:allyl chloride:NaOH and reaction time. DMSO/TBAF was found to be an efficient reaction medium for the preparation of highly functionalized samples from spruce sulfite pulp with degree of polymerization of about 500 even in a scale of 50 g. The allyl cellulose samples were characterized by means of FTIR- and NMR spectroscopy. Size exclusion chromatography revealed negligible polymer degradation during synthesis and purification of the samples.     

Molecular weight effect on the obtainment of parallel and perpendicular orientation in thermotropic poly(diethylene glycol <Emphasis Type="Italic">p,p′</Emphasis>-bibenzoate)

Summary The effect of molecular weight on the uniaxial orientation process has been analyzed in two samples of thermotropic poly(diethylene glycol p,p′-bibenzoate), evaluating the influence of that parameter on the type of orientation obtained. Several strain rates and deformation temperatures have been tested in order to map out the conditions for obtaining the two different kinds of orientation. The results show that in the lower molecular weight PDEB sample (M_w=31200) it is rather easy to get exclusively perpendicular “anomalous” orientation, with the molecular axes aligned transversely to the stretching direction. However, it is extremely difficult to obtain 100% parallel “normal” orientation. On the contrary, either type of orientation or a mixture of them can be easily developed for the higher molecular weight PDEB sample (M_w=102900).     

Synthesis of TiO<Subscript>2</Subscript> Hybrid Molecular Imprinted Polymer for Ethofumesate Linked by Silane Coupling Agent

TiO₂ hybrid molecular imprinted polymer (MIP) for ethofumesate using methacrylic acid (MAA) as the functional monomer and silane coupling agent 3-(trimethoxysilyl) propylmethacrylate (KH570) as organic–inorganic connective bridge was synthesized via photo-excitation method. Hydrogen bond was proved to act between MAA and ethofumesate for pre- and post-polymerization binding properties as testified by UV spectrometric method. KH570 modified TiO₂ nanoparticles were prepared via sonochemical reaction, which can accelerate hydrolysis, increase collision chance for the reactive system and improve the dispersion of the nanoparticles. Scanning electron microscope (SEM), transmission electron microscope (TEM), binding and the adsorption kinetics experiments as well as thermogravimetric analysis (TGA) were employed for characterization. The results indicated that the hybrid MIP revealed a larger surface area and more ordered imprinting cavities with improved thermal stability compared to organic-only MIP. Furthermore, faster adsorption kinetics and enhancive adsorption capacity were achieved, which made it promising in chemical sensor applications.     

Ring‐opening polymerization of D,L‐lactide by rare earth 2,6‐dimethylaryloxide

Ring‐opening polymerization of D,L ‐lactide (LA) has been successfully carried out by using rare earth 2,6‐dimethylaryloxide (Ln(ODMP)₃) as single component catalyst or initiator for the first time. The effects of different rare earth elements, solvents, monomers and catalyst concentration as well as polymerization temperature and time on the polymerization were investigated. The results show that La(ODMP)₃ exhibits higher activity to prepare poly(D,L ‐lactide) (PLA) with a viscosity molecular weight of 4.5 × 10⁴ g mol^?1 and the conversion of 97 % at 100 °C in 45 min. The catalytic activity of Ln(ODMP)₃ has following sequence: La > Nd > Sm > Gd > Er > Y. A kinetic study has indicated that the polymerization is first order with respect to both monomer and catalyst concentration. The apparent activation energy of the polymerization of LA with La(ODMP)₃ is 69.6 kJ mol^?1. The analyses of polymer ends indicate that the LA polymerization proceeds according to ‘coordination–insertion’ mechanism with selective cleavage of the acyl–oxygen bond of the monomer. Copyright © 2004 Society of Chemical Industry     

Performance modeling and evaluation of data/voice services in wireless networks

Application-level performance is a key to the adoption and success of the CDMA 2000. To predict this performance in advance, a detailed end-to-end simulation model of a CDMA network is built to include application traffic characteristics, network architecture, network element details using the proposed simulation methodology. We assess the user-perceived application performance when a RAN and a CN adopt different transport architectures such as ATM and IP. To evaluate the user-perceived quality of voice service, we compare the end-to-end packet delay for different vocoder schemes such as G.711, G.726 (PCM), G.726 (ADPCM), and vocoder bypass scheme. By the simulation results, the vocoder bypass scenario shows 30% performance improvement over the others. We also compare the quality of voice service with and without DPS scheduling scheme. We know that DPS scheme keep the voice delay bound even if the service traffic is high. For data packet performance, HTTP v.1.1 shows better performance than that of HTTP v.1.0 due to the pipelining and TCP persistent connection. We may conclude that IP transport technology is better solution for higher FER environment since the packet overhead of IP is smaller than that of ATM for web browsing data traffic, while it shows opposite effect to the small size voice packet in RAN architecture. We show that the 3G-1X EV-DO system gives much better packet delay performance than 3G-1X RTT. The main conclusion is that end-to-end application-level performance is affected by various elements and layers of the network and thus it must be considered in all phases of the development process. Jae-Hyun Kim He received the B.S., M.S., and Ph.D. degrees, all in computer science and engineering, from Hanyang University, Ansan, Korea, in 1991, 1993, and 1996 respectively. In 1996, he was with the Communication Research Laboratory, Tokyo, Japan, as a Visiting Scholar. From April 1997 to October 1998, he was a post-doctoral fellow at the department of electrical engineering, University of California, Los Angeles. From November 1998 to February 2003, he worked as a member of technical staff in Performance Modeling and QoS management department, Bell laboratories, Lucent Technologies, Holmdel, NJ. He has been with the department of electrical engineering, Ajou University, Suwon, Korea, as an assistant professor since 2003. His research interests include QoS issues and cross layer optimization for high-speed wireless communication. Dr. Kim was the recipient of the LGIC Thesis Prize and Samsung Human-Tech Thesis Prize in 1993 and 1997, respectively. He is a member of the Korean Institute of Communication Sciences (KICS), Korea Institute of Telematics and Electronis (KITE), Korea Information Science Society (KISS), and IEEE. Hyun-Jin Lee received the B.S. degree in electrical engineering from Ajou University, Suwon, Korea, in 2004, and is working toward the M.S. degree and Ph. D. degree in electrical engineering at Ajou University. He has been awarded Samsung Human-Tech Thesis Prize in 2004. His research interests QoS, especially network optimization and wireless packet scheduling. He is a member of the KICS. Sung-Min Oh received the B.S. and M. S. degrees in electrical engineering form Ajou University, Suwon, Korea, in 2004, and is working toward the Ph. D. degree in electrical engineering at Ajou University. His research interests QoS performance analysis and 4G network. He is a member of the KICS. Sung-Hyun Cho received his B.S., M.S., and Ph.D. in computer science and engineering from Hanyang University, Korea, in 1995, 1997, and 2001, respectively. From 2001 to 2005, he has been with Samsung Advanced Institute of Technology, where he has been engaged in the design and standardization of MAC and upper layers of B3G, IEEE 802.16e, and WiBro systems. He is currently a MAC part leader in the telecommunication R&D center of Samsung Electronics. His research interests include 4G air interface design, radio resource management, cross layer design, and handoff in wireless systems.     

Is there a direct relationship between oral astringency and human salivary protein binding?

For decades, it is believed that astringency is due to the polyphenol-induced complexation of proline-rich salivary proteins in the oral cavity. In order to compare for the first time the human sensory threshold concentrations and the salivary protein binding activity of a series of astringent stimuli, human saliva protein was incubated for 5 min at 37 °C in the presence of astringent food-derived compounds and, after micro-centrifugation, the amount of the target molecules in the supernatant was quantitatively determined by HPLC-UV/Vis. Significant protein binding was observed for (−)-epigallocatechin-3-gallate, (−)-gallocatechin-3-gallate, (+)-gallocatechin, and (−)-catechin-3-gallate, all of which containing at least one galloyl moiety in the molecule and exhibiting rather high sensory thresholds of more than 200 μmol/L. In comparison, (+)-catechin and procyanidin B2, both lacking in any galloyl function, showed only comparatively low binding activity and, most interestingly, quercetin-3-O-α-l-rhamnopyranosyl-(1 → 6)-β-d-glucopyranoside and 3-carboxymethyl-indole-1-N-β-d-glucopyranoside did not show any protein binding at all, although the later N- and O-glycosides exhibited extraordinarily low sensory threshold concentrations of less than 0.001 and 0.0003 μmol/L, respectively. The data give some first evidence that the quantity of the non-bound, “free” astringent stimulus in the saliva liquid might be more closely related to the sensory perception of astringency than the amount complexed or precipitated by proteins. It is therefore questionable as to whether oral perception of astringency is related to the complexation and/or precipitation of salivary proteins.     

Synthesis and characterization of zeolite NaY from rice husk silica

Rice husk silica (RHS) in amorphous phase with 98% purity was prepared from a waste rice husk from rice milling by leaching with hydrochloric acid and calcination. The RHS was used effectively as a silica source for the synthesis of zeolite Y in sodium form (NaY). The zeolite in pure phase was obtained from a two-step synthetic route in which the starting gels were mixed, aged for 24 h at room temperature and crystallized for 24 h at 90 °C. The diameter of single crystal particles from a scanning electron microscope was approximately 1.0 μm, whereas the average particle diameter from laser diffraction particle size analyzer was approximately 10 μm because of the agglomeration of small crystals. Longer crystallization time in this route resulted in a mixed phase containing NaY and zeolite P in sodium form (NaP). In addition, a one-step synthetic route (no aging) was studied and the product was also a mixed phase zeolite.     

Highly ordered anodic alumina nanotemplate with about 14 nm diameter

A novel method for the fabrication of highly ordered nanopore arrays with very small diameter of 14 nm was demonstrated by using low-temperature anodization. Two-step anodization was carried out at 25 V, sulfuric acid concentration of 0.3 M, and electrolyte temperature of −15 °C. After anodization, a regular pore array with mean diameter of 14 nm and interpore distance of 65 nm was formed. The pore diameter and regular arrangement were confirmed by scanning electron microscopy (SEM) and fast Fourier transformation (FFT), respectively. The present results strongly suggest that the diameter of pores in a highly ordered alumina template can be reduced by lowering the anodization temperature.     

Multi-site phase transfer catalyst assisted radical polymerisation of glycidyl methacrylate using potassium peroxydisulphate as initiator – a kinetic study

In this work, the kinetics and mechanism of free-radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxydisulphate (PDS) as water soluble initiator in the presence of synthesized 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (TBMABDC) as multi-site phase transfer catalyst (MPTC) was studied. The polymerisation reactions were carried out under inert and unstirred conditions at constant temperature of 60 ± 1°C in cyclohexane/water biphase media. The role of concentrations of monomer, initiator, catalyst and volume fraction of aqueous phase, solvent polarity and temperature on the rate of polymerisation (Rp) was ascertained. The order with respect to monomer and initiator was found to be unity. The order with respect to catalyst was found to be 0.51. The rate of polymerisation is independent of ionic strength and pH of the medium. However, an increase in the polarity of solvent has slightly increased the Rp value. Based on the results obtained, a suitable kinetic scheme has been proposed to account for the experimental observations and its significance discussed.     

Effect of surfactants and liquid hydrocarbons on gas hydrate formation rate and storage capacity

Hydrate formation rate plays an important role in making hydrates for the storage and transport of natural gas. Micellar surfactant solutions were found to increase gas hydrate formation rate and storage capacity. With the presence of surfactant, hydrate could form quickly in a quiescent system and the energy costs of hydrate formation reduced. Surfactants (an anionic surfactant, a non‐ionic surfactant and their mixtures) and liquid hydrocarbons (cyclopentane and methylcyclohexane) were used to improve hydrate formation. The experiments of hydrate formation were carried out in the pressure range 3.69–6.82 MPa and the temperature range 274.05–277.55 K. The experimental pressures were kept constant during hydrate formation in each experimental run. The effect of anionic surfactant (sodium dodecyl sulphate (SDS)) on natural gas storage in hydrates is more pronounced compared to a non‐ionic surfactant (dodecyl polysaccharide glycoside (DPG)). The induction time of hydrate formation was reduced with the presence of cyclopentane (CP). Cyclopentane and methylcyclohexane (MCH) could increase hydrate formation rate, but reduced hydrate storage capacity The higher methylcyclohexane concentration, the lower the hydrate storage capacity. Copyright © 2003 John Wiley & Sons, Ltd.