Preparation of polymer-supported gold nanoparticles based on resins containing ionic liquid-like fragments: easy control of size and stability

Crosslinked polymers containing covalently attached functional sites with chemical structures related to those present in ILs and having macroscopic properties very similar to the ones of the corresponding bulk ILs can be advantageously applied to the preparation of gold nanoparticles (AuNPs). The size and morphology of the resulting metal nanoparticles (MNPs) can be easily modulated through a proper combination of the synthetic method used for the generation of the NPs and the structural elements of the polymer. Additionally, the resulting supported AuNPs are demonstrated to be stable for at least eight months with the vials open to the atmosphere. Several synthetic methodologies have been studied, as well as different structural parameters for the functional polymers. Those include the chemical nature (anions and cations) and loading of the ionic liquid-like fragments and the morphology of the polymeric matrix. The results obtained show the potential to prepare supported AuNPs with narrow size distributions and small diameters that can have potential interest for application in different fields.     

Structure of CdS/SiO2 Nanocomposites: Influence of the Precursor and Cd Concentration

The influence of using TMOS or TEOS in the formation of CdS quantum dots in a silica matrix have been studied by X-ray absorption spectroscopy (XAS). The amount of Cd-S bonds have been monitored as a function of the nominal Cd concentration. The relative amount of CdS crystals depends on the precursor. The use of TEOS is not recommended because it gives a poor yield, especially for high Cd concentration. A discussion of the influence of CdS concentration in matrices from TMOS is carried out from structural models created from their pore volume distribution. The mean pore size becomes smaller and the size distribution more uniform when CdS concentration increases but the nanocrystals of low CdS nominal content present a more efficient quantum confinement.     

Some Basics on Privacy Techniques,Anonymization and their Big Data Challenges

With the progress in the information and communication fields, new opportunities and technologies for statistical analysis, knowledge discovery, data mining, and many other research areas have emerged, together with new challenges for privacy and data protection. Nowadays several personal records are kept in computerized databases. Personal data is collected and kept in census databases, medical databases, employee databases, among others. There has always been an asymmetry between the benefits of computerized databases and the rights of individual data subjects. Some data protection principles can be derived from the legal framework. In this survey, we present some basic cryptographic and non-cryptographic techniques that may be used for enhancing privacy, we focus mainly on anonymization in databases and networks, discuss some differences and interactions among the well-known models of k-anonymity and differential privacy and finally present some challenges to privacy that come from big data analytics.     

Estimating critical values for testing the i.i.d. in standardized residuals from GARCH models in finite samples

Taking into account that the BDS test—which is used as a misspecification test applied to standardized residuals from the GARCH(1,1) model—is characterized by size distortion and departure from normality in finite samples, this paper obtains the critical values for the finite sample distribution of the BDS test. We focus on bootstrap simulation to avoid the sampling uncertainty of parameter estimation and make use of estimated response surface regressions (RSR) derived from the experimental results. We consider an extensive grid of models to obtain critical values with the results of the bootstrap experiments. The RSR used to estimate them is an artificial neural network (ANN) model, instead of the traditional linear regression models. Specifically, we estimate critical values by using a bootstrap aggregated neural network (BANN) and by employing functions of the sample size and parameters used in the experiment as the embedding dimension and proximity parameters in the BDS statistic, GARCH parameters and even the q-quantiles of the BDS distributions. The main results confirm that the sample size and BDS parameters play a role in size distortion. Finally, an empirical application to three price indexes is performed, to highlight the differences between decisions made using the asymptotic or our predicted critical values for the BDS test in finite samples.     

Analytical formulas for complex permittivity of periodic composites. Estimation of gain and loss enhancement in active and passive composites

ABSTRACT

The asymptotic homogenization method is applied to complex dielectric periodic composites. An equivalence to coupled dielectric problems with real coefficients is shown. This is similar to a piezoelectric problem: an out-plane mechanical displacement and an in-plane electric potential establishing a correspondence principle. Closed-form formulas for the complex dielectric effective tensor in the case of a square array of circular inclusions embedded in a matrix are given. These formulas are written in terms of a real and symmetric matrix which facilitates the implementation of the computational scheme. We also get similar formulas for multilayered complex dielectric composites. The real closed-form formulas are advantageous for estimating gain and loss enhancement properties of active and passive composites in certain volume fraction intervals. Numerical computations are performed and the results are compared with other approaches showing the usefulness of the obtained formulas. This may be of interest in the context of metamaterials.     

能量连续传递的超分子人工光捕获系统构筑及其在光催化反应中应用

光捕获系统在自然界光合作用过程中起着至关重要的作用.模拟自然界的光捕获体系,在生物成像、发光器件、光催化以及解决人类面临的能源问题等方面均具有重要意义[1].目前,在水相中构筑高效的人工光捕获系统已取得一系列重要进展[2].然而,为了更好地理解并模拟自然界中以多通道信息通讯为特征的捕光天线系统[3],构筑具有多步连续能量转移特征并能实现光能到化学能转化的人工光捕获体系仍然是一项具有挑战性的工作.     

Shedding Light on the Origin of Solid-State Luminescence Enhancement in Butterfly Molecules

Different molecular strategies have been carefully evaluated to produce solid-state luminescence enhancement (SLE) in compounds that show dark states in solution. A set of α-phenylstyrylarene derivatives with a butterfly shape have been designed and synthesised, for the first time, with the aim of improving the solid-state fluorescence emission of their parent styrylarene compounds. Although these butterfly molecules are not fluorescent in solution, one of them (1,2,4,5-tetra(α-phenylstyryl)benzene) exhibits a fluorescence quantum yield as high as 68 % in a drop-cast sample and 31 % in its crystalline form. In contrast, 1,3,5-tris(α-phenylstyryl)benzene and 4,6-bis(α-phenylstyryl)pyrimidine do not show SLE. A range of fluorescence spectroscopy experiments and DFT calculations were carried out to unravel the origin of different photophysical behaviour of these compounds in the solid state. The results indicate that a rational strategy to control the SLE effect in luminogens depends on a delicate balance between molecular properties and inter-/intramolecular interactions in the solid state.     

Square Wave Adsorptive Stripping Voltammetry Determination of Chlorpyriphos in Irrigation Agricultural Water

This work describes the electroanalytical determination of Chlorpyriphos pesticide in natural waters using hanging mercury drop electrode allied to square wave adsorptive cathodic stripping voltammetry. The best responses were obtained in Britton?Robinson buffer solutions at pH 2.0, using a frequency of 100 s^–1, a scan increment of 5 mV, a square wave amplitude of 25 mV and an accumulation potential of–0.4 V during 60 s. Therefore, voltammetric responses showed the presence of one well-defined and irreversible reduction peak, at–1.08 V vs. Ag/AgCl/KCl 1.0 M, which involves two electrons in the reduction of carbon?nitrogen bond in the N-heterocyclic system with the participation of protonation equilibrium preceding the electron transfer reaction. Analytical curves were constructed and compared to similar curves performed by gas chromatograph coupled to a selective nitrogen?phosphorus detector, which demonstrates that the proposed methodology is suitable for determining contamination by Chlorpyriphos in complex samples.     

A polynomial expression for the Owen value in the maintenance cost game

The class of maintenance cost games was introduced in 2000 to deal with a cost allocation problem arising in the reorganization of the railway system in Europe. The main application of maintenance cost games regards the allocation of the maintenance costs of a facility among the agents using it. To that aim it was first proposed to utilize the Shapley value, whose computation for maintenance cost games can be made in polynomial time. In this paper, we propose to model this cost allocation problem as a maintenance cost game with a priori unions and to use the Owen value as a cost allocation rule. Although the computation of the Owen value has exponential complexity in general, we provide an expression for the Owen value of a maintenance cost game with cubic polynomial complexity. We finish the paper with an illustrative example using data taken from the literature of railways management.