Sustainable Diels–Alder syntheses in imidazolium ionic liquids

An effective and simple protocol for the Diels–Alder reactions catalyzed and mediated by ionic liquid in conjunction with Lewis acid was studied. Diels–Alder adduct of the reaction of 1,4-benzoquinone with isoprene and 2,3-dimethyl-1,3-butadiene was obtained in good to excellent yields within the time span of 5.00–4.00 min under microwave irradiation. Due to the excellent activity of 2,3-dimethyl-1,3-butadiene as a diene, its efficiency was further analyzed by performing against four different dienophiles under various reaction conditions. The ionic liquid, 3-methyl-1-octyl-imidazolium tetrachloroaluminate mixed with Lewis acids, could be recycled and reused for consecutive cycles. The recovered ionic liquid in conjunction with Lewis acid displayed almost similar activity without any significant loss. This system is an essential upgrade and related to the reactions consuming common organic solvents at high temperatures and longer duration. Diels–Alder reactions under solventless conditions have also been investigated for the aforesaid reactions.     

Influence of molecular weight and degree of segregation on local segmental dynamics of ordered block copolymers

Experiments in the context of block copolymer electrolyte materials have observed intriguing dependence of the ionic conductivities upon the polymer molecular weight and the degree of segregation between the blocks. Such results have been partly rationalized by invoking the spatial extent of dynamical inhomogeneities that manifest in ordered phases of block copolymers comprised of a rubbery and a glassy block. Motivated by such observations, we use molecular dynamics simulations to study the extent of spatial inhomogeneities in segmental dynamics of lamellar diblock copolymer systems where the blocks possess different mobilities. We probed the local average relaxation times and the dynamical heterogeneities as a function of distance from the interface. Our results suggest that the relaxation times of rubbery segments are strongly influenced by both the spatial proximity to the interface and the relative mobility of the glassy segments. Scaling of our results indicate that the interfacial width of the ordered phases serves as the length scale underlying the spatial inhomogeneities in segmental dynamics of the fast monomers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 859–864     

Design of bicontinuous donor/acceptor morphologies for use as organic solar cell active layers

In recent works, we demonstrated the achievement of bicontinuous donor/acceptor morphologies by the addition of conjugated block copolymers to a blend of conjugated homopolymer donors and fullerene acceptors. However, the domain sizes resulting in experiments were much larger than those of interest for high‐performance organic solar cells. Moreover, a significant concentration of fullerene acceptors was present in the donor domains. Here, we utilize simulations to study the bicontinuous donor/acceptor morphologies that result for different parametric conditions. Using such results, we provide guidelines for how to blend polymer materials to give rise to bicontinuous phases with the smaller and more compositionally pure domains that are desirable for organic photovoltaic applications. Our results can be generalized to treat a large range of donor and acceptor monomers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 884–895     

Stereoselective synthesis of syn-β-amino esters using the TiCl4/R3N reagent system

The reactions of benzaldehyde imines and esters with the TiCl₄/R₃N reagent system give syn-β-amino esters as the major products in 38-87% yields.     

Strategies for the Dynamic Integration of Combinatorial Synthesis and Screening

Selection and amplification of only those components with the desired property–the integration of combinatorial chemistry and screening makes this possible. If the components of a combinatorial library are in a reversible equilibrium, the desired components can be selected and amplified by shifting the equilibrium of the mixture (see schematic representation).     

可移动半无限垂直圆柱体温度交变振荡时对MHD自由对流的影响

不可压缩粘性流体,流过可移动、温度交变振荡的半无限垂直圆柱体时,对MHD自由对流影响的数值解进行了研究.应用Crank-Nicolson型的隐式有限差分方法,求解无量纲、不稳定、非线性、耦合的偏微分控制方程.在不同参数下研究速度、温度和浓度分布的变化,还分析了局部及平均的表面摩擦力、Nusselt数和Sherwood数,并以图形形式给出.所得结果与其他文献的结果比较,有着很好的一致性.     

A Pseudo-Global Optimization Approach with Application to the Design of Containerships

In this paper, we present a new class of pseudo-global optimization procedures for solving formidable optimization problems in which the objective and/or constraints might be analytically complex and expensive to evaluate, or available only as black-box functions. The proposed approach employs a sequence of polynomial programming approximations that are constructed using the Response Surface Methodology (RSM), and embeds these within a branch-and-bound framework in concert with a suitable global optimization technique. The lower bounds constructed in this process might only be heuristic in nature, and hence, this is called a pseudo-global optimization approach. We develop two such procedures, each employing two alternative branching techniques, and apply these methods to the problem of designing containerships. The model involves five design variables given by the design draft, the depth at side, the speed, the overall length, and the maximum beam. The constraints imposed enforce the balance between the weight and the displacement, a required acceptable length to depth ratio, a restriction on the metacentric height to ensure that the design satisfies the Coast Guard wind heel criterion, a minimum freeboard level as governed by the code of federal regulations (46 CFR 42), and a lower bound on the rolling period to ensure sea-worthiness. The objective function seeks to minimize the required freight rate that is induced by the design in order to recover capital and operating costs, expressed in dollars per metric ton per nautical mile. The model formulation also accommodates various practical issues in improving the representation of the foregoing considerations, and turns out to be highly nonlinear and nonconvex. A practical test case is solved using the proposed methodology, and the results obtained are compared with those derived using a contemporary commercialized design optimization tool. The prescribed solution yields an improved design that translates to an estimated increase in profits of about $18.45 million, and an estimated 27% increase in the return on investment, over the life of the ship.     

Characterization of high ionic conducting PVAc–PMMA blend-based polymer electrolyte for electrochemical applications

A solid polymer blend electrolyte is prepared using poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) polymers with different molecular weight percentage (wt%) of ammonium thiocyanate (NH₄SCN) by solution casting technique with tetrahydrofuran (THF) as a solvent. The structural, morphological, vibrational, thermal and electrical properties of the prepared polymer blend electrolytes have been studied. The incorporation of NH₄SCN into the polymeric matrix causes decrease in the degree of crystallinity of the samples. The complex formation between the polymer and salt has been confirmed by FTIR technique. The increase in T _g with increase in salt concentration has been investigated. The maximum conductivity of 3.684?×?10^?3 S cm^?1 has been observed for the composition of 70PVAc/30PMMA/30 wt% of NH₄SCN at 303 K. This value of ionic conductivity is five orders of magnitude greater than that of 70PVAc/30PMMA polymer membrane. Dielectric and transport studies have been done. The highest conducting polymer electrolyte is used to fabricate proton battery with the configuration Zn/ZnSO₄·7H₂O (anode) ||polymer electrolyte||PbO₂/V₂O₅ (cathode). The open circuit voltage of the fabricated battery is 1.83 V, and its performance has been studied.     

Surface and transport studies on La0.7Ba0.3MnO3:SnO2 bilayer

We report on study of morphology, optical contrast and transport characteristics of La_0.7Ba_0.3MnO₃ (LBMO) manganite thin films bilayered with SnO₂ on Si (0 0 1) substrate, synthesized using pulsed laser deposition system. X-ray diffraction study reveals that both LBMO and SnO₂ show polycrystalline growth over the substrate. Atomic force microscopy shows interesting pyramidal structures of LBMO of size ∼2 μm × 1 μm × 0.1 μm. On the other hand, SnO₂ grows in the form of close packed cylindrical clusters of ∼200 nm radius. Near-field optical microscopy (NSOM) study using 532 nm laser reveal that optical NSOM output intensity in LBMO is four times less than SnO₂ signal. Transport characterizations show that this bilayer configuration exhibit non-linear current-voltage characteristics from 300 upto 50 K. The nature becomes linear below this temperature. The results project the system as a promising candidate in non-conventional device category in the area of spintronics.     

Studies on modified anode polymer hydrogen sensor

An improved polymer electrolyte membrane (PEM) fuel cell based amperometric hydrogen sensor that operates at room temperature has been developed. The electrolyte used in the sensor is PVA/H₃PO₄ blend, which is a proton conducting solid polymer electrolyte. A blend of palladium and platinum coated on the membrane is used as anode and platinum as cathode. The sensor functions as a fuel cell, H₂/Pd-Pt//PVA-H₃PO₄//Pt/O₂, and the short circuit current is found to be linearly related to the hydrogen concentration. The present study aims at investigating the dependence of sensor behaviour on the anode composition. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.