Synthesis and copolymerization of new phosphorus‐containing acrylates

Two phosphorus‐containing acrylate monomers were synthesized from the reaction of ethyl α‐chloromethyl acrylate and t‐butyl α‐bromomethyl acrylate with triethyl phosphite. The selective hydrolysis of the ethyl ester monomer with trimethylsilyl bromide (TMSBr) gave a phosphonic acid monomer. The attempted bulk polymerizations of the monomers at 57–60 °C with 2,2′‐azobisisobutyronitrile (AIBN) were unsuccessful; however, the monomers were copolymerized with methyl methacrylate (MMA) in bulk at 60 °C with AIBN. The resulting copolymers produced chars on burning, showing potential as flame‐retardant materials. Additionally, α‐(chloromethyl)acryloyl chloride (CMAC) was reacted with diethyl (hydroxymethyl)phosphonate to obtain a new monomer with identical ester and ether moieties. This monomer was hydrolyzed with TMSBr, homopolymerized, and copolymerized with MMA. The thermal stabilities of the copolymers increased with increasing amounts of the phosphonate monomer in the copolymers. A new route to highly reactive phosphorus‐containing acrylate monomers was developed. A new derivative of CMAC with mixed ester and ether groups was synthesized by substitution, first with diethyl (hydroxymethyl)phosphonate and then with sodium acetate. This monomer showed the highest reactivity and gave a crosslinked polymer. The incorporation of an ester group increased the rate of polymerization. The relative reactivities of the synthesized monomers in photopolymerizations were determined and compared with those of the other phosphorous‐containing acrylate monomers. Changing the monomer structure allowed control of the polymerization reactivity so that new phosphorus‐containing polymers with desirable properties could be obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2207–2217, 2003     

Interpretive approach to collective effects of electrons in multicenter problems

Interpretive theoretical tools prove valuable in guiding the analysis of experiments in the realm of atomic clusters. Here, we review basic elements of an analytic approach that makes it possible to find and visualize the effective electrostatic potential and Coulomb correlations in multicenter problems. To illustrate the utility of these concepts we apply them to exploring molecular-doped metallic clusters. This study is aiming at a systematic, visual assessment of changes induced in screening, Coulomb correlation and effective potential by varying the charge of the electronegative impurity and its position in the cluster cage.     

A new algorithm for fixed design regression and denoising

In this paper, we present a new algorithm to estimate a regression function in a fixed design regression model, by piecewise (standard and trigonometric) polynomials computed with an automatic choice of the knots of the subdivision and of the degrees of the polynomials on each sub-interval. First we give the theoretical background underlying the method: the theoretical performances of our penalized least-squares estimator are based on non-asymptotic evaluations of a mean-square type risk. Then we explain how the algorithm is built and possibly accelerated (to face the case when the number of observations is great), how the penalty term is chosen and why it contains some constants requiring an empirical calibration. Lastly, a comparison with some well-known or recent wavelet methods is made: this brings out that our algorithm behaves in a very competitive way in term of denoising and of compression.     

Inorganic Sol-Gel Preparation of Medium Sized Microparticles of Li2TiO3 from TiCl4 as Tritium Breeding Material for Fusion Reactors

Microspheres of Li₂TiO₃ were fabricated by a classical, inorganic sol-gel process from commercially available TiCl₄. Elaborated process consists of the following main steps: (1) dissolving of TiCl₄ in concentrated aqueous HCl and addition of LiOH; (2) formation of sol emulsion in 2-ethylhexanol-1 containing the surfactant SPAN-80 (EH); (3) gelation of emulsion drops by extraction of water with partially dehydrated EH; (4) impregnation of gel to Li:Ti molar ratio MR = 2; (5) thermal treatment at 1200°C in order to receive chloride free product. This temperature can be significantly lowered (to 750°C) by dechlorination starting solution TiCl₄ by chemical treatment of the with nitric acid to form of nitrate-stabilized titania sols. Tritium release from sol-gel made Li₂TiO₃ microspheres were found very close to that observed for other traditional materials, however for the first sample process starts slightly earlier.     

Click chemistry in materials synthesis. III. Metal‐adhesive polymers from Cu(I)‐catalyzed azide–alkyne cycloaddition

1,2,3‐Triazole‐based polymers generated from the Cu(I)‐catalyzed cycloaddition between multivalent azides and acetylenes are effective adhesive materials for metal surfaces. The adhesive capacities of candidate mixtures of azide and alkyne components were measured by a modified peel test, using a customized adhesive tester. A particularly effective tetravalent alkyne and trivalent azide combination was identified, giving exceptional strength that matches or exceeds the best commercial formulations. The addition of Cu catalyst was found to be important for the synthesis of stronger adhesive polymers when cured at room temperature. Heating also accelerated curing rates, but the maximum adhesive strengths achieved at both room temperature and high temperature were the same, suggesting that crosslinking reaches the same advanced point in all cases. Polytriazoles also form adhesives to aluminum, but copper is bound more effectively, presumably because active Cu(I) ions may be leached from the surface to promote crosslinking and adhesion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5182–5189, 2007     

Tail probabilities of the limiting null distributions of the Anderson–Stephens statistics

For the purpose of testing the spherical uniformity based on i.i.d. directional data (unit vectors) z_i, i=1,…,n, Anderson and Stephens (Biometrika 59 (1972) 613–621) proposed testing procedures based on the statistics S_max=max_u S(u) and S_min=min_u S(u), where u is a unit vector and nS(u) is the sum of squares of u′z_i's. In this paper, we also consider another test statistic S_range=S_max−S_min. We provide formulas for the P-values of S_max, S_min, S_range by approximating tail probabilities of the limiting null distributions by means of the tube method, an integral-geometric approach for evaluating tail probability of the maximum of a Gaussian random field. Monte Carlo simulations for examining the accuracy of the approximation and for the power comparison of the statistics are given.     

线性规划的符号跟踪算法

分析了只含一个约束条件的线性规划最优基变量的特征，将其运用到搜寻含m个约束条件的线性规划的最优基变量，从而提出了线性规划的符号跟踪算法，为线性规划求解提供了新途径。     

模糊半群上的模糊同余及其扩张

给出模糊半群上的模糊同余的概念，并进一步研究它的一些基本代数性质。同时研究带有模糊半群上的模糊同余扩张性质(FCEPF)的半群类，得到一个半群有模糊半群上的模糊同余扩张性质、有模糊同余扩张性质(FCEP)、有同余扩张性质(CEP)三个条件是等价的。     

Spectral Analysis of Powers of the Operator (Vf)(x)=q(x)∫0 xw(t)f(t),dt

Mathematical Notes -     

Security Applications of Optical Face Recognition System: Access Control in E-Learning

The educational system has gradually shifted from a face-to-face to an e-learning system, which has become prevalent in advanced countries with the advance of information technology, and connection of global networks. Accordingly, a growing demand is emerging for more reliable individual certification with technical precision in order to measure and record learning achievements and credentials of participants. The present system has a limit in terms of registration capacity, therefore, its accuracy has often been questioned. Against this background, an individual certification system is proposed particularly for access control in e-learning. Under our proposed system, a compact optical correlator for facial recognition is employed. This correlator was previously tested for of biometrics authentication accuracy and proved highly reliable, having recorded remarkably low error rates (below 1%). The recorded error rate is sufficiently robust that the system itself can be regarded as a valid and practical viable attestation system.