Reactivity of valganciclovir in aqueous solution

The rates of hydrolysis of valganciclovir to ganciclovir and L-valine and isomerization of the R and S diastereomers of valganciclovir in aqueous buffer solution from pH 3.8 to 11.5 were determined at 37 degrees C. The kinetics of hydrolysis were first order for at least two half-lives in neutral and basic solutions. In acidic solutions where less than 10% degradation occurred, the rate of hydrolysis was determined assuming a first-order loss in drug. At 37 degrees C and pH 7.08, the half life is 11 h. The maximum stability at the pH values studied occurred at pH 3.81 with a half life of 220 days. The kinetics of the approach to equilibrium for the isomerization were first order and the ratio of the R:S isomer at equilibrium was 52:48. Isomerization was approximately 10 fold faster than hydrolysis over the pH range studied with a half-life at pH 7.01 of 1 h. The maximum stability toward isomerization (t1/2>533 h) occurs at a pH below 3.8. The pH-rate profile for the hydrolysis and the isomerization reaction are best described by hydroxide ion catalyzed mechanisms. In acidic and neutral solutions, the hydroxide reacts with the protonated form of the drug, while in basic solutions, the hydroxide reacts with the neutral form of the drug.     

Preparation of a selective receptor for ephedrine for the development of an optical spot test for the detection of ephedrine in human urine using stabilized in air lipid films with incorporated receptor

The present technique describes the preparation of a selective receptor for ephedrine and a simple sensitive spot optical test for the rapid one-shot detection of ephedrine in human urine using lipid films with an incorporated receptor that are synthesized by a chemical reaction with a methacrylate polymer on a glass fiber filter. The selective receptor was synthesized using a resorcin[4]arene receptor and by transforming all the -OH groups into methoxy groups. The lipid films without this receptor provided fluorescence under a UV lamp. The use of the receptor in these films quenched this fluorescence, and the color became similar to that of the filters without the lipid films. A drop of aqueous solution of ephedrine provided a "switching on" of the fluorescence, which allows the rapid detection of this stimulant in human urine at the levels of 10(-8) M concentrations. The effect of potent interferences (i.e., proteins, lipids, ascorbic aid, glucose, leucine, glycine, tartrate, citrate, bicarbonate, and caffeine) was examined. The results showed no interferences from these compounds in concentration levels usually found in human urine samples. Dopamine was also investigated as a potent interfering agent, and the results have shown that the transformation of the hydroxy to methoxy groups has altered the selectivity of the receptor. This species does not cause interference at concentration levels lower than 10(-6) M. A drop of urine containing ephedrine provided also a "switching on" of the fluorescence, which allows the rapid detection of this stimulant in human urine at the levels of 10(-8) M concentrations. The reproducibility of the method was checked in approximately 100 samples, and all of them were found to provide similar results. Note that the colors of the filters remain stable for periods of more than 2 months.     

A modified K-means algorithm for circular invariant clustering

Several important pattern recognition applications are based on feature vector extraction and vector clustering. Directional patterns are commonly represented by rotation-variant vectors F/sub d/ formed from features uniformly extracted in M directions. It is often desirable that pattern recognition algorithms are invariant under pattern rotation. This paper introduces a distance measure and a k-means-based algorithm, namely, circular k-means (CK-means) to cluster vectors containing directional information, such as F/sub d/, in a circular-shift invariant manner. A circular shift of F/sub d/ corresponds to pattern rotation, thus, the algorithm is rotation invariant. An efficient Fourier domain representation of the proposed measure is presented to reduce computational complexity. A split and merge approach (SMCK-means), suited to the proposed CK-means technique, is proposed to reduce the possibility of converging at local minima and to estimate the correct number of clusters. Experiments performed for textural images illustrate the superior performance of the proposed algorithm for clustering directional vectors F/sub d/, compared to the alternative approach that uses the original k-means and rotation-invariant feature vectors transformed from F/sub d/.     

Parametric Formant Modelling and Transformation in Voice Conversion

This paper presents a method for the estimation and mapping of parametric models of speech resonance at formants for voice conversion. The spectral features at formants that contribute to voice characteristics are the trajectories of the frequencies, the bandwidths and intensities of the resonance at formants. The formant features are extracted from the poles of a linear prediction (LP) model of speech. The statistical distributions of formants are modelled by a two-dimensional hidden Markov model (HMM) spanning the time and frequency dimensions. Experimental results are presented which show a close match between HMM-based formant models and the histograms of formants. For voice conversion two alternative methods are explored for mapping the formants of a source speaker to those of a target speaker. The first method is based on an adaptive formant-tracking warping of the frequency response of the LP model and the second method is based on the rotation of the poles of the LP model of speech. Both methods transform all spectral parameters of the resonance at formants of the source speaker towards those of the target speaker. In addition, the issues affecting the selection of the warping ratios for the mapping functions are investigated. Experimental results of formant estimation and perceptual evaluation of voice morphing based on parametric formant models are presented.     

Polyurethane networks from formiated soy polyols: Synthesis and mechanical characterization

Polyurethanes can be prepared using polyols obtained from vegetable oils in natura, such as castor oil, or from functionalized vegetable oils, such as hydroxylated soybean oil. These polyurethanes have different valuable properties, determined by their chemical composition and cross-linking density. In this study, soy epoxy polyols with different OH contents were prepared through a one-step reaction using the method of in situ performic acid generation. Polyols with OH functionalities from 1.9 to 3.2 were reacted in bulk with different diisocyanates at a NCO/OH molar ratio of 0.8 and 60°C for 24 h. Mechanical properties of the polyurethanes were determined by dynamic mechanical thermal analysis, hardness (Shore A), and swelling measurements. Polymer networks with glass-transition temperatures (T _g ) from −13 to 48°C were obtained. We observed that the higher the OH functionality of the polyols, the higher the T _g and cross-linking density of the polyurethane network. The influence of diisocyanate structure (rigid or flexible chain), curing temperature, and curing reaction time on mechanical properties was also investigated.     

Geophysical imaging of stimulated microbial biomineralization

Understanding how microorganisms influence the physical and chemical properties of the subsurface is hindered by our inability to observe microbial dynamics in real time and with high spatial resolution. Here, we investigate the use of noninvasive geophysical methods to monitor biomineralization at the laboratory scale during stimulated sulfate reduction under dynamic flow conditions. Alterations in sediment characteristics resulting from microbe-mediated sulfide mineral precipitation were concomitant with changes in complex resistivity and acoustic wave propagation signatures. The sequestration of zinc and iron in insoluble sulfides led to alterations in the ability of the pore fluid to conduct electrical charge and of the saturated sediments to dissipate acoustic energy. These changes resulted directly from the nucleation, growth, and development of nanoparticulate precipitates along grain surfaces and within the pore space. Scanning and transmission electron microscopy (SEM and TEM) confirmed the sulfides to be associated with cell surfaces, with precipitates ranging from aggregates of individual 3-5 nm nanocrystals to larger assemblages of up to 10-20 microm in diameter. Anomalies in the geophysical data reflected the distribution of mineral precipitates and biomass over space and time, with temporal variations in the signals corresponding to changes in the aggregation state of the nanocrystalline sulfides. These results suggest the potential for using geophysical techniques to image certain subsurface biogeochemical processes, such as those accompanying the bioremediation of metal-contaminated aquifers.     

Exploring the design space of reliable multicast protocols for wireless mesh networks

Many important applications in wireless mesh networks require reliable multicast communication, i.e., with 100% packet delivery ratio (PDR). Previously, numerous multicast protocols based on automatic repeat request (ARQ) have been proposed to improve the packet delivery ratio. However, these ARQ-based protocols can lead to excessive control overhead and drastically reduced throughput. In this paper, we present a comprehensive exploration of the design space for developing high-throughput, reliable multicast protocols that achieve 100% PDR.Motivated by the fact that 802.11 MAC layer broadcast, which is used by most wireless multicast protocols, offers no reliability, we first examine if better hop-by-hop reliability provided by unicasting the packets at the MAC layer can help to achieve end-to-end multicast reliability. We then turn to end-to-end solutions at the transport layer. Previously, forward error correction (FEC) techniques have been proved effective for providing reliable multicast in the Internet, by avoiding the control packet implosion and scalability problems of ARQ-based protocols. In this paper, we examine if FEC techniques can be equally effective to support reliable multicast in wireless mesh networks. We integrate four representative reliable schemes (one ARQ, one FEC, and two hybrid) originally developed for the Internet with a representative multicast protocol ODMRP and evaluate their performance.Our experimental results via extensive simulations offer an in-depth understanding of the various choices in the design space. First, compared to broadcast-based unreliable ODMRP, using unicast for per-hop transmission only offers a very small improvement in reliability under low load, but fails to improve the reliability under high load due to the significantly increased capacity requirement which leads to congestion and packet drop. Second, at the transport layer, the use of pure FEC can significantly improve the reliability, increasing PDR up to 100% in many cases, but can be inefficient in terms of the number of redundant packets transmitted. In contrast, a carefully designed ARQ–FEC hybrid protocol, such as RMDP, can also offer 100% reliability while improving the efficiency by up to 38% compared to a pure FEC scheme. To our best knowledge, this is the first in-depth study of high-throughput, reliable multicast protocols that provide 100% PDR for wireless mesh networks.     

A Guard Code Scheme for Handover Traffic Management in WCDMA Systems

A key performance indicator of mobile wireless networks is failure probability of handover calls. In this paper, we propose a Call Admission Control policy which prioritizes handover calls over new calls in WCDMA systems. The OVSF code occupancy of the system is modeled by a Markov chain and the differentiation between handover and new calls is performed at the code level by introducing a “guard code” scheme. The scheme belongs to the well-known family of guard channel schemes and reserves some code capacity to favor the continuation of handover calls over the new calls. As the management of the general case is intractable, we solve certain numerical instances of the problem and manage to calculate several performance metrics like new call blocking and handover failure probabilities and code utilization. We complete our study with simulation results in the case of higher OVSF code tree capacity.

Optimal rate allocation for production and injection wells in an oil and gas field for enhanced profitability

An oil and gas field requires careful operational planning and management via production optimization for increased recovery and long-term project profitability. This article addresses the challenge of production optimization in a field undergoing secondary recovery by water flooding. The field operates with limited processing capacity at the surface separators, pipeline pressure constraints, and water injection constraints; an economic indicator (net present value, NPV) is used as the objective function. The formulated optimization framework adequately integrates slow-paced subsurface dynamics using reservoir simulation, and fast-paced surface dynamics using sophisticated multiphase flow simulation in the upstream facilities. Optimization of this holistic long-term model is made possible by developing accurate second-order polynomial proxy models at each time step. The resulting formulation is solved as a nonlinear program using commercially available solvers. A comparative analysis is performed using MATLAB's fmincon solver and the IPOPT solver for their robustness, speed, and convergence stability in solving the proposed problem. By implementing two synthetic case studies, our mathematical programming approach determines the optimal production and injection rates of all wells and further demonstrates considerable improvement to the NPV obtained by simultaneously applying the tools of streamline, reservoir, and surface facility simulation for well rate allocation via systematic NLP optimization.