Azobenzene‐Functionalized Cage Silsesquioxanes as Inorganic–Organic Hybrid,Photoresponsive, Nanoscale,Building Blocks

Mono‐ and octa‐azobenzene‐functionalized cage silsesquioxanes were easily synthesized by the reaction of 4‐bromoazobenzene with monovinyl‐substituted octasilsesquioxane and cubic octavinylsilsesquioxane through the Heck coupling reaction. Excited‐state energies obtained from time‐dependent density functional theory (TDDFT) and the CAM‐B3LYP functional correlate very well with experimental trans–cis photoisomerization results from UV/Vis spectroscopy. These azobenzene‐functionalized cages exhibit good thermal stability and are fluorescent with maximum emission at approximately 400 nm, making them potential materials for blue‐light emission.     

Melting behaviors,crystallization kinetics,and spherulitic morphologies of poly(butylene succinate) and its copolyester modified with rosin maleopimaric acid anhydride

This article investigated the melting behaviors, crystallization kinetics, and spherulitic morphologies of poly(butylene succinate) (PBS) and its copolyester (PBSR) modified with rosin maleopimaric acid anhydride, using wide‐angle X‐ray diffraction, differential scanning calorimeter (DSC), and polarized optical microscope. Subsequent DSC scans of isothermally crystallized PBS and PBSR exhibited two melting endotherms, respectively, which was due to the melt‐recrystallization process occurring during the DSC scans. The equilibrium melting point of PBSR (125.9 °C) was lower than that of PBS (139 °C). The commonly used Avrami equation was used to describe the isothermal crystallization kinetics. For nonisothermal crystallization studies, the model combining Avrami equation and Ozawa equation was employed. The result showed a consistent trend in the crystallization process. The crystallization rate was decreased, the perfection of crystals was decreased, the recrystallization was reduced, and the spherulitic morphologies were changed when the huge hydrogenated phenanthrene ring was added into the chain of PBS. The activation energy (ΔE) for the isothermal crystallization process determined by Arrhenius method was 255.9 kJ/mol for PBS and 345.7 kJ/mol for PBSR. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 900–913, 2006     

Synthesis and aggregation behavior of <Emphasis Type="Italic">N</Emphasis>-succinyl-o-carboxymethylchitosan in aqueous solutions

A simple and novel method was developed to successfully synthesize N-succinyl-O-carboxymethylchitosan (NSOCMCS) using N-acylation of chitosan with succinic anhydride. The NSOCMCS structure was characterized by Fourier transform infrared and ¹H nuclear magnetic resonance. The aggregation behaviors of NSOCMCS were studied using fluorescence spectroscopy, dynamic light scattering, and atomic force microscopy techniques. The critical aggregation concentration of NSOCMCS in water was determined to be 0.2–0.3 mg/ml. The apparent hydrodynamic radium of an NSOCMCS aggregate was dependent on the concentration. The aggregates demonstrated a much swollen association conformation in aqueous solution. The possible aggregation mechanisms for the NSOCMCS in water are discussed. Moreover, a driving force to form an open aggregation morphology was revealed in this study. Aggregation behaviors are important physicochemical properties of NSOCMCS, which impact the potential application in the biomedical field.     

Curing reaction characteristics and phase behaviors of biphenol type epoxy resins with phenol novolac resins

Diglycidyl ether of 4,4′-dihydroxybiphenol (BPDGE) is a liquid crystalline epoxy. The biphenyl epoxy (diglycidyl ether of 3,3′,5,5′-tetramethyl-4,4′-biphenyl, TMBPDGE) has found great applications in plastic encapsulated semiconductor packaging. Phenol novolac (PN) was used as curing agent. The reaction kinetics of BPDGE/PN and TMBPDGE/PN systems in the presence of triphenylphosphine (TPP) were characterized by an isoconversional method under dynamic conditions using differential scanning calorimetry (DSC) measurements. The results showed that the curing of epoxy resins involves different reaction stages and the values of activation energy are dependent on the degree of conversion. The effects of curing temperature on their phase structure have been investigated with polarized optical microscopy and Wide-angle X-ray diffraction. With proper curing process, BPDGE showed a nematic phase when cured with PN.     

The Electrochemical Behavior of α‐Ketoglutarate at the Hanging Mercury Drop Electrode in Acidic Aqueous Solution and Its Practical Application in Environmental and Biological Samples

The voltammetric behavior of α‐ketoglutarate (α‐KG) at the hanging mercury drop electrode (HMDE) has been investigated in acetate buffer solution. Under the optimum experimental conditions (pH 4.5, 0.2 M NaAc‐HAc buffer solution), a sensitive reductive wave of α‐KG was obtained by linear scan voltammetry (LSV) and the peak potential was ?1.18 V (vs. SCE), which was an irreversible adsorption wave. The kinetic parameters of the electrode process were α=0.3 and k_s=0.72 1/s. There was a linear relationship between peak current i_{p, α‐KG} and α‐KG concentration in the range of 2×10^?6–8×10^?4 M α‐KG. The detection limit was 8×10^?7 M and the relative standard deviation was 2.0% (C_α‐KG=8×10^?4 M, n=10). Applications of the reductive wave of α‐KG for practical analysis were addressed as follows: (1) It can be used for the quantitative analysis of α‐KG in biological samples and the results agree well with those obtained from the established ultraviolet spectrophotometric method. (2) Utilizing the complexing effect between α‐KG and aluminum, a linear relationship holds between the decrease of peak current of α‐KG Δi_p and the added Al concentration Cequation/tex2gif-inf-5.gif in the range of 5.0×10^?6–2.5×10^?4 M. The detection limit was 2.2×10^?6 M and the relative standard deviation was 3.1% (Cequation/tex2gif-inf-6.gif=4×10^?5 M, n=10). It was successfully applied to the detection of aluminum in water and synthetic biological samples with satisfactory results, which were consistent with those of ICP‐AES. (3) It was also applied to study the effect of Al^III on the glutamate dehydrogenase (GDH) activity in the catalytically reaction of α‐KG+NH +NADH?L ‐glutamate+NAD⁺+H₂O by differential pulse polarography (DPP) technique. By monitoring DPP reductive currents of NAD⁺ and α‐KG, an elementary important result was found that Al could greatly affect the activity of GDH. This study could be attributed to intrinsic understanding of the aluminum's toxicity in enzyme reaction processes.     

Spectroscopic studies on 2,3,4,5-tetraphenylpyrylium salts with and without silver (I)-bridged structures

Two novel phenylated pyrylium compounds, silver (I)-bridged 2,3,4,5-tetraphenylpyrylium perchlorate (P1) and its silver (I)-free pyrylium ligand (P2) were prepared from 1,2,3,4-tetraphenylcyclopentadiene to examine their spectroscopic behaviors. The UV/vis absorption and fluorescent emission spectra of P1 and P2, measured in three solvents (acetonitrile, dichloromethane and toluene), reveal that the photophysical behaviors are closely related to silver (I) fragment, and strongly dependent on solvent polarity. In polar acetonitrile, P1 displays longer absorption wavelength and much lower fluorescent emission intensity than P2, although they exhibit much similarity in shape. In contrast, in nonpolar toluene, while P2 shows an apparent absorption band at 338 nm, P1 displays a tail-like line without absorption band observed. All the spectra obtained indicate a better coplanarity and a stronger intra-molecular charge transfer in P1 due to the effect of silver (I) fragment. Additionally, the 1H NMR spectra of P1 and P2, which were recorded under the same conditions, indicate that the silver (I) fragment reinforces pyrylium ring's capacity to localize the formal positive charge within the heterocyclic ring.     

Phenomenology of nonlocal cellular automata

Dynamical systems with nonlocal connections have potential applications to economic and biological systems. This paper studies the dynamics of nonlocal cellular automata. In particular, all two-state, three-input nonlocal cellular automata are classified according to the dynamical behavior starting from random initial configurations and random wirings, although it is observed that sometimes a rule can have different dynamical behaviors with different wirings. The nonlocal cellular automata rule space is studied using a mean-field parametrization which is ideal for the situation of random wiring. Nonlocal cellular automata can be considered as computers carrying out computation at the level of each component. Their computational abilities are studied from the point of view of whether they contain many basic logical gates. In particular, I ask the question of whether a three-input cellular automaton rule contains the three fundamental logical gates: two-input rules AND and OR, and one-input rule NOT. A particularly interesting edge-of-chaos nonlocal cellular automaton, the rule 184, is studied in detail. It is a system of coupled selectors or multiplexers. It is also part of the Fredkin's gate—a proposed fundamental gate for conservative computations. This rule exhibits irregular fluctuations of density, large coherent structures, and long transient times.     

Preparation and Tribological Behaviors of Lubricants—Oil Based on Modified Microbial Oil with Nano-Schiff Base Copper Complex

A W/O microemulsion reactor was used to prepare four kinds of modified lubricants: (i) modified lubricant 1, modified epoxidized microbial oil + rape oil in volume ratio of 1:1; (ii) modified lubricant 2, modified esterified microbial oil + rape oil in volume ratio of 1:3; (iii) modified lubricant 3, modified epoxidized rape oil; and (iv) modified lubricant 4, modified PAO. The individual modified lubricants were further modified with 0%, 0.5%, 1%, and 2% content of nano-Schiff base copper complex (nano-SBCC). A microtribometer was used to evaluate the friction coefficient between ball/flat point contacts immersed in the modified lubricants and operated in reciprocating and linear sliding mode. A comparison of the values of the friction coefficient with the lubricants further modified with nano-SBCC with those of their individual 0% nano-SBCC counterparts indicated significant decrease: (i) almost 19.18% was obtainable for the modified lubricant 1 with 2% of nano-Schiff base copper complex, (ii) almost 16.5% was obtainable for the modified lubricant 2 with 0.5% of nano-Schiff base copper complex; (iii) almost 7.42% was obtainable for the modified lubricant 3 with 1% of nano-SBCC; and (iv) almost 7.01% was obtainable for the modified lubricant 4 with 0.5% of nano-SBCC. These suggested that the addition of nano-Schiff base copper complex can efficiently decrease the friction coefficient of epoxidized or esterified microbial oil. Analyses of two-dimensional images, average profiles (across the mid-section y = 0 of the reciprocating sliding path), and three-dimensional topographies by confocal white light microscope for the worn surfaces of flats immersed in modified lubricant 1 and modified lubricant 2 suggested better wear-resistance of the modified lubricant 2 than that of the modified lubricant 1. The ability of wear resistance for the modified lubricant became better with the increasing content of nano-Schiff base copper complex from 0% to 2%. The study revealed the modification of epoxidized microbial oil + rape oil (1:1 volume ratio) and esterified microbial oil + rape oil (1:3 volume ratio) with Cu(II) chelate of bis(salicylaldehyde)ethylenediamine, reducing the magnitude of friction and wear because of their respective wear self-repairing ability. Such self-repairing ability furnishes the suitability of epoxidized microbial oil or esterified microbial oil to be effectively modified by nano-Schiff base copper complex and to substitute ordinary base oil as a mixture with rape oil.     

Transient transition behaviors of fractional-order simplest chaotic circuit with bi-stable locally-active memristor and its ARM-based implementation

This paper proposes a fractional-order simplest chaotic system using a bi-stable locally-active memristor. The characteristics of the memristor and transient transition behaviors of the proposed system are analyzed, and this circuit is implemented digitally using ARM-based MCU. Firstly, the mathematical model of the memristor is designed, which is nonvolatile, locally-active and bi-stable. Secondly, the asymptotical stability of the fractional-order memristive chaotic system is investigated and some sufficient conditions of the stability are obtained. Thirdly, complex dynamics of the novel system are analyzed using phase diagram, Lyapunov exponential spectrum, bifurcation diagram, basin of attractor, and coexisting bifurcation, coexisting attractors are observed. All of these results indicate that this simple system contains the abundant dynamic characteristics. Moreover, transient transition behaviors of the system are analyzed, and it is found that the behaviors of transient chaotic and transient period transition alternately occur. Finally, the hardware implementation of the fractional-order bi-stable locally-active memristive chaotic system using ARM-based STM32F750 is carried out to verify the numerical simulation results.     

A vectorial algorithm with finite element method for prediction of powder segregation in metal injection molding

The design of the mold and the choice of the injection parameters for metal injection molding (MIM) is required to maintain homogeneity of the filled mixture. However, powder segregation is unavoidable in MIM because of the significant difference in densities of the metallic powder and the polymer binder. To achieve an effective prediction of segregation effect, a biphasic model based on mixture theory is employed. The viscous behaviors of each phase and the interaction coefficient between the flows of the two phases should be determined. The solution of two coupled Navier–Stokes equations results in a tremendous computation effort. The previous development of an explicit algorithm makes the biphasic simulation much faster than that of the classic methods. However, it is strongly desired to reduce or even eliminate the numerous global solutions for pressure fields at each time step. Hence, a new vectorial algorithm is proposed and developed to perform the simulation only by vectorial operations. It provides the anticipated efficiency in the simulation of biphasic modeling, and the advantage to use the classic elements of equal‐order interpolations. Some results produced by the two algorithms are compared with the experimental values to validate the new vectorial algorithm. Copyright © 2012 John Wiley & Sons, Ltd.