Evaluation of a complete HPLC solvent optimization system involving piece-wise quadratic modelling

Summary Interpretive methods are accepted to give the best possible results for selectivity optimization in HPLC. However the methods are very complex, and most work so far has been detailed academic studies. This paper describes an evaluation of a complete integrated system incorporating peak labelling, modelling of retention behaviour and calculation of response surfaces, with particular emphasis on the retention modelling. The peak labelling section has been discussed previously.A piece-wise quadratic function is investigated for the modelling of retention times across an isoeluotropic plane to effect selectivity optimization in HPLC. This requires 10 data-points on the isoeluotropic plane. The predicted global optimum and local optima are evaluated by comparison of calculated and experimental retention data, for a nine component sample. Seven interstitial points, distributed across the whole plane between the data-points, are similarly evaluated for a related sample. The typical error (in retention time) is less than 2%, often 1%, and the maximum error is 4.2%. At the global optimum the error was found be less than 1.3% for all 9 peaks.     

RELATIONSHIPS BETWEEN X—H STRETCHING OVERTONE FREQUENCIES AND BOND LENGTHS/BOND ANGLES

A relationship between the X-H (X = N, O, C, and so on) equilibrium bond length in a Morse oscillator and the X-H stretching overtone frequency shifts is obtained theoretically. We use the equation to discuss the empirical linear relationships that have been proposed for heterocyclics, alkanes and fluorinated benzenes. On the other hand, a unified relationship between the X-H bond angles and the experimental quantities (ω(?) and the coupling strength λ) is also presented for XH2, XH, and XH4 molecules or molecular fragments. Calculations of X-H bond angles for a number of molecules show that the results from our equations are in excellent agreement with the experimental values. Also we can extract the information of relative magnitude of bond coupling force field.     

Mixed strategy solutions forN-person quadratic games

Mixed strategy -equilibrium points are given forN-person games with cost functions consisting of quadratic, bilinear, and linear terms and strategy spaces consisting of closed balls in Hilbert spaces. The results are applied to linear-quadratic differential games with no information and quadratic integral constraints on the control functions.This work was supported by a Commonwealth of Australia, Postgraduate Research Award.     

Oligothienylenevinylenes incorporating 3,4-ethylenedioxythiophene (EDOT) units

A new series of π-conjugated oligomers based on various combinations of thiophene and EDOT units and double bonds has been synthesized by Wittig-Horner reactions from phosphonate anions carrying EDOT or bis-EDOT units. Optical and electrochemical results evidence the crucial role of the EDOT moiety for modulating the electronic properties of the oligomers. The insertion of bis-EDOT unit in the middle of the molecule leads to a self-rigidification of the conjugated system due to non covalent S?O intramolecular interactions. The strong electron donor effect of the EDOT units explains the determining role of the relative position of the EDOT units on the localization and stabilization of the positive charges in the radical cation or dication states.     

Significance of Non-isothermal Kinetic Data. A statistical study

Arrhenius parameters values, in non-isothermal kinetic vaporisation processes for a series of compounds with related structures, have been calculated. This was made using a method of calculation that allows to find the most probable vaporisation mechanisms. According to this method DTG curves were compared with some theoretical ones reported in literature, whose shape results to be only a function of the mechanisms. In this way the choice of the mathematical functions which can be inserted in the kinetic equations, was influenced by the shape of the DTG plots and other thermal analysis signals thus allowing to choose the most probable mechanisms. The kinetic parameters derived from these mechanisms were compared, using statistical analysis, with those obtained from another method of calculation based on ‘a priori’ vaporisation mechanism chosen for the investigated liquid–gas transition. The standard deviations of the slope and of the intercept, together with the standard deviation and the square correlation coefficient (r ²) of the linear regression equations related to the mechanisms of the two methods were calculated. Student t-test, Fisher F-test, confidence intervals (c.i.) and residuals valueswere also given. Statistical analysis shows that the mechanisms obtained with the former method (diffusive and geometrical models) and the related Arrhenius parameters result to be more significant (in terms of probability) than the corresponding quantities of the latter for which a first-order model was chosen. This revised version was published online in August 2006 with corrections to the Cover Date.     

Blind Speech Watermarking Method with Frame Self-Synchronization Based on Spread-Spectrum Using Linear Prediction Residue

State-of-the-art speech watermarking techniques enable speech signals to be authenticated and protected against any malicious attack to ensure secure speech communication. In general, reliable speech watermarking methods must satisfy four requirements: inaudibility, robustness, blind-detectability, and confidentiality. We previously proposed a method of non-blind speech watermarking based on direct spread spectrum (DSS) using a linear prediction (LP) scheme to solve the first two issues (inaudibility and robustness) due to distortion by spread spectrum. This method not only effectively embeds watermarks with small distortion but also has the same robustness as the DSS method. There are, however, two remaining issues with blind-detectability and confidentiality. In this work, we attempt to resolve these issues by developing an approach called the LP-DSS scheme, which takes two forms of data embedding for blind detection and frame synchronization. We incorporate blind detection with frame synchronization into the scheme to satisfy blind-detectability and incorporate two forms of data embedding process, front-side and back-side embedding for blind detection and frame synchronization, to satisfy confidentiality. We evaluated these improved processes by carrying out four objective tests (PESQ, LSD, Bit-error-rate, and accuracy of frame synchronization) to determine whether inaudibility and blind-detectability could be satisfied. We also evaluated all combinations with the two forms of data embedding for blind detection with frame synchronization by carrying out BER tests to determine whether confidentiality could be satisfied. Finally, we comparatively evaluated the proposed method by carrying out ten robustness tests against various processing and attacks. Our findings showed that an inaudible, robust, blindly detectable, and confidential speech watermarking method based on the proposed LP-DSS scheme could be achieved.     

Low-Complexity Alternatives to the Optimal Linear Coding Scheme for Transmitting ARMA Sources

In the era of the Internet of Things, there are many applications where numerous devices are deployed to acquire information and send it to analyse the data and make informed decisions. In these applications, the power consumption and price of the devices are often an issue. In this work, analog coding schemes are considered, so that an ADC is not needed, allowing the size and power consumption of the devices to be reduced. In addition, linear and DFT-based transmission schemes are proposed, so that the complexity of the operations involved is lowered, thus reducing the requirements in terms of processing capacity and the price of the hardware. The proposed schemes are proved to be asymptotically optimal among the linear ones for WSS, MA, AR and ARMA sources.     

Chemometric Analysis of Urinary Volatile Organic Compounds to Monitor the Efficacy of Pitavastatin Treatments on Mammary Tumor Progression over Time

Volatile organic compounds (VOCs) in urine are potential biomarkers of breast cancer. Previously, our group has investigated breast cancer through analysis of VOCs in mouse urine and identified a panel of VOCs with the ability to monitor tumor progression. However, an unanswered question is whether VOCs can be exploited similarly to monitor the efficacy of antitumor treatments over time. Herein, subsets of tumor-bearing mice were treated with pitavastatin at high (8 mg/kg) and low (4 mg/kg) concentrations, and urine was analyzed through solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS). Previous investigations using X-ray and micro-CT analysis indicated pitavastatin administered at 8 mg/kg had a protective effect against mammary tumors, whereas 4 mg/kg treatments did not inhibit tumor-induced damage. VOCs from mice treated with pitavastatin were compared to the previously analyzed healthy controls and tumor-bearing mice using chemometric analyses, which revealed that mice treated with pitavastatin at high concentrations were significantly different than tumor-bearing untreated mice in the direction of healthy controls. Mice treated with low concentrations demonstrated significant differences relative to healthy controls and were reflective of tumor-bearing untreated mice. These results show that urinary VOCs can accurately and noninvasively predict the efficacy of pitavastatin treatments over time.     

单A直和子空间

引入单直和子空间的概念,证明了线性空间可唯一分解为单直和子空间的直和,并且给出了计算方法.     

解大型线性方程组的ATOR方法

本文提出了一种数值求解大型稀疏线性方程组Ax=b的具有三个参数的迭代法,我们称之为ATOR法,并且指出,熟知的Jacobi法、Gauss-Seidel法,SOR法,AOR法和TOR法为其特例.同时,我们对具有某些性质的系数矩阵A——Hermite正定矩阵、H-矩阵、L-矩阵和对角占优矩阵,讨论了ATOR法的收敛性以及给出了迭代矩阵谱半径的表达式和上界估计。