Synthesis and characterization of poly{2-[3-(1H-pyrrol-2-yl)phenyl]-1H-pyrrole} and its copolymer with EDOT

A pyrrole-functionalized monomer 2-[3-(1H-pyrrol-2-yl)phenyl]-1H-pyrrole (PyPhPy) was synthesized. The structure of monomer was investigated by Nuclear Magnetic Resonance (¹H NMR) and Fourier Transform Infrared (FTIR) spectroscopy. The chemical polymerization of PyPhPy (CPyPhPy) was realized using FeCl₃ as the oxidant. The electrochemical oxidative polymerization of polymer P(PyPhPy) and its copolymer with 3,4-ethylenedioxythiophene poly(2-[3-(1H-pyrrol-2-yl)phenyl]-1H-pyrrole-co-3,4-ethylenedioxythiophene) [P(PyPhPy-co-EDOT)] were achieved via potentiodynamic method by using NaClO₄/LiClO₄ as the supporting electrolyte in CH₃CN. Characterizations of the resulting polymers were performed by cyclic voltammetry (CV), FTIR, scanning electron microscopy (SEM), UV-Visible spectrophotometry (UV-Vis) and thermogravimetry analyses (TGA). Electrical conductivity of CPyPhPy, P(PyPhPy), and P(PyPhPyco-EDOT) were measured by four-probe technique.     

Constancy maximization based weight optimization in high dimensional model representation for multivariate functions

High Dimensional Model Representation (HDMR) method is a technique that represents a multivariate function in terms of less-variate functions. Even though the method has a finite expansion, to determine the components of this expansion is very expensive due to integration based natures of the components. Hence, the HDMR expansion is generally truncated at certain multivariance level and such approximations are produced to represent the given multivariate function approximately. The weight function selection becomes an important issue for the HDMR based applications when it is desired to give different importances to function values at different points. An appropriately chosen weight function may increase the quality of the approximation incredibly. This work aims at a multivariate weight function optimization to obtain high quality approximations through the HDMR method to represent multivariate functions. The proposed optimization considers constancy measurer maximization which produces a quadratic vector equation to be solved. Another contribution of this work is to use a recently developed method, fluctuation free integration, with HDMR, to solve this equation easily. This work is an extension of a previous work about weight optimization in HDMR for univariate functions.     

Adsorption of Cr(VI) on ureolytic mixed culture from biocatalytic calcification reactor

Ca-rich water and wastewater have caused problems in water use, wastewater reuse and the operations of reactors treating Ca-rich wastewater. Nowadays, reuse of wastewaters is fast gaining importance as water sources have been polluted. Therefore, the concept of biocatalytic calcification reactors (BCR) based on urea hydrolysis, pH increase and calcite production has been studied to remove Ca from wastewaters. This biological process produces significant amounts of waste sludge. In the present study, Cr(VI) adsorption on the ureolytic mixed culture (UMC) waste by-product from BCR was investigated to evaluate its potential for metal removal. The biosorption process was investigated using equilibrium batch tests and the data were fit to the Langmuir, Freundlich and Temkin isotherm models. The Cr(VI) ion concentration dependence of sorption (1-100 mg/L) could be fit to the Langmuir isotherm model. Monolayer adsorption capacity, qm (mg/g), of the adsorbent was 8.67 and the Langmuir constant b (L/mg) was 0.881. Based on the obtained results, the waste UMC appears to be a potential biosorbent for the removal of Cr(VI) from wastewater, although its adsorptive capacity is lower than those of other biosorbents.     

Determination of pharmacokinetics of flurbiprofen in Pakistani population using modified HPLC method

Pharmacokinetics of flurbiprofen has been studied in different populations, especially in Caucasian. However, there are very few studies reported from Eastern part of world. Previous studies suggested that genetic and environmental factors may cause inter-individual differences in flurbiprofen disposition, so we investigated the pharmacokinetics of flurbiprofen in Pakistani subjects. A single oral dose of 100 mg of flurbiprofen was administered to 22 healthy male Pakistani adults after overnight fasting for 10 h. Periodical blood sampling was done at 0.25, 0.5, 0.75, 1, 1.5, 2, 2.5, 3, 4, 5, 6, 7, 8, 10, 12, and 24 h after dosing. Plasma concentration of flurbiprofen was determined by a modified high-performance liquid chromatography method, which was simple, sensitive, less time consuming and economical with ordinary internal standard. The method was validated according to ICH guidelines and was found to be sensitive, accurate and precise. The pharmacokinetic parameters observed in Pakistani subjects when compared with other populations (USA, UK, Canadian, French, and Indian) did not show considerable ethnic differences. However, one subject's data was suggestive of being poor metabolizer of flurbiprofen which supports the presence of CYP2C9 polymorphism contributing to inter-individual differences in flurbiprofen disposition. Pharmacogenomic studies are needed to verify this hypothesis.     

Stability of aqueous silica nanoparticle dispersions

In this study, we present quantification methods for nanoparticle stability analysis using non-intrusive analytical techniques: attenuated total reflectance, Fourier transform infrared (ATR-FTIR) spectroscopy, ultraviolet–visible (UV–vis) spectrophotometer, zeta potential analyses, and dynamic light scattering (DLS). We use these techniques to study the stability of silica nanoparticle dispersions and the effects of pH, temperature, and electrolytes that would be encountered in oil field brines in a reservoir. Spectral analysis of the Si–O bond at wavenumber of 1110 cm⁻¹ with the ATR-FTIR indicates a structural change on the surface of silica particles as the dispersion pH changes, which agrees with zeta potential measurements. We define a critical salt concentration (CSC) for different salts, NaCl, CaCl₂, BaCl₂, and MgCl₂, above which the silica dispersion becomes unstable. Three distinct stages of aggregation occur in the presence of salt: clear dispersed, turbid, and separated phases. Divalent cations Mg²⁺, Ca²⁺, and Ba²⁺ are more effective in destabilizing silica nanoparticle dispersion than the monovalent cation Na⁺. The CSC for Na⁺ is about 100 times more than for Ca²⁺, Ba²⁺, and Mg²⁺. Among the divalent cations studied, Mg²⁺ is the most effective in destabilizing the silica particles. The CSC is independent of silica concentration, and lowers at high temperature.     

Combination of Oral Vitamin D3 with Photodynamic Therapy Enhances Tumor Cell Death in a Murine Model of Cutaneous Squamous Cell Carcinoma

Photodynamic therapy (PDT), in which 5‐ALA (a precursor for protoporphyrin IX, PpIX) is administered prior to exposure to light, is a nonscarring treatment for skin cancers. However, for deep tumors, ALA‐PDT is not always effective due to inadequate production of PpIX. We previously developed and reported a combination approach in which the active form of vitamin D₃ (calcitriol) is given systemically prior to PDT to improve PpIX accumulation and to enhance PDT‐induced tumor cell death; calcitriol, however, poses a risk of hypercalcemia. Here, we tested a possible strategy to circumvent the problem of hypercalcemia by substituting natural dietary vitamin D₃ (cholecalciferol; D₃) for calcitriol. Oral D₃ supplementation (10 days of a 10‐fold elevated D₃ diet) enhanced PpIX levels 3‐ to 4‐fold, and PDT‐mediated cell death 20‐fold, in subcutaneous A431 tumors. PpIX levels and cell viability in normal tissues were not affected. Hydroxylated metabolic forms of D₃ were only modestly elevated in serum, indicating minimal hypercalcemic risk. These results show that brief oral administration of cholecalciferol can serve as a safe neoadjuvant to ALA‐PDT. We suggest a clinical study, using oral vitamin D₃ prior to PDT, should be considered to evaluate this promising new approach to treating human skin cancer.     

Solving the dynamic capacitated location-routing problem with fuzzy demands by hybrid heuristic algorithm

In this paper, the dynamic capacitated location-routing problem with fuzzy demands (DCLRP-FD) is considered. In the DCLRP-FD, facility location problem and vehicle routing problem are solved on a time horizon. Decisions concerning facility locations are permitted to be made only in the first time period of the planning horizon but, the routing decisions may be changed in each time period. Furthermore, the vehicles and depots have a predefined capacity to serve the customers with altering demands during the time horizon. It is assumed that the demands of customers are fuzzy variables. To model the DCLRP-FD, a fuzzy chance-constrained programming is designed based upon the fuzzy credibility theory. To solve this problem, a hybrid heuristic algorithm (HHA) with four phases including the stochastic simulation and a local search method are proposed. To achieve the best value of two parameters of the model, the dispatcher preference index (DPI) and the assignment preference index (API), and to analyze their influences on the final solution, numerical experiments are carried out. Moreover, the efficiency of the HHA is demonstrated via comparing with the lower bound of solutions and by using a standard benchmark set of test problems. The numerical examples show that the proposed algorithm is robust and could be used in real world problems.     

Evolution of the Fiber Density in Biological Tissues

An important challenge in the field of biomechanics is to understand and to model the properties of fibrous tissues. We consider a matrix-fiber composite for which the matrix microstructure and its mechanical properties are taken to be constant. The initial fiber distribution is assumed to be unstructured and the mechanical properties of the fibers evolve during deformation. Further we assume that the fiber creation rate is constant while the fiber degeneration is stretch-dependent. In particular, this study investigates the change of the fiber orientation density when a sudden simple shear is applied to the material. The fiber orientation density depends on the current deformation, the history of the deformation, and the deformation state of the fibers at the time of their creation. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A comparative study on the mode of interaction of different nanoparticles during MALDI‐MS of bacterial cells

We propose the benefits of preincubation during nanoparticle‐assisted bacterial analysis, where the bacteria are grown along with the nanoparticles. We were able to obtain a two to ten fold enhancement of bacterial signals in 3 h compared to the generally used methodology followed in previous literature. The previous literature method required a long time (18 h) to obtain such an enhancement. We probe the interactions of two bacteria, Staphylococcus aureus and Pseudomonas aeruginosa, with Ag, NiO, Pt TiO₂ and ZnO nanoparticles via transmission electron microscopy, ultraviolet spectroscopy and matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry (MS). Based on these results, we propose a mechanism for interaction of these five nanoparticles with bacteria. Two mechanisms were observed for the interactions: (1) Mechanism A is proposed for the Pt and NiO NPs which functioned based on affinity for bacterial cells. (2) Mechanism B was proposed for the bactericidal NPs such as TiO₂, ZnO and Ag NPs. The results indicate that the success of the unmodified NPs in MALDI‐MS bacterial studies lies in following the ideal protocol for incubation at the ideal concentrations. Copyright © 2013 John Wiley & Sons, Ltd.     

Selective Expression of a Carbazole-Phenothiazine Derivative Leads to Dual-mode AIEE,TADF and Distinctive Mechanochromism

In this article, we report a newly designed D−A−D’ derivative (CNCzPTZ), which displays selective expression of chromophores. This enables CNCzPTZ with solvatochromism, rare dual-mode AIEE properties, solid-state dual-emissions with phosphorescence and distinctive mechanochromism.CNCzPTZ exhibits dual-mode AIEE properties, since the emission band abruptly shifts from 550 nm to 500 nm as the water fraction increases. In the crystalline state, CNCzPTZ demonstrated dual emission bands of 478 nm and 538 nm.CNCzPTZ shows distinctive mechanochromic property in the solid state due to the planarization.