Ab-initio study of long-period superstructures and anti-phase boundaries in Al-rich γ-TiAl (L10)-based alloys

In this work, we report first-principles investigation of structural stability of all experimentally observed ordered long-period superstructures (LPSs), viz., r-Al₂Ti, h-Al₂Ti, Al₅Ti₃ along with Al₅Ti₃′, Al₁₁Ti₇ and Al₃Ti₂ LPSs, which are observed only as short-range ordered clusters at nanoscale level in Al-rich TiAl-based alloys. We adopt a procedure based on space-filling tiling arrangement of ordered Ti₂Al, Ti₃Al, Ti₄Al motifs and their combination along with a symmetry analysis programme to determine the unit cell and the crystallographic information of Al₅Ti₃′, Al₁₁Ti₇ and Al₃Ti₂ LPSs in terms of L1₀ fcc unit cell. First-principles calculations are performed to further refine these crystallographic parameters (Wyckoff positions and lattice parameters) obtained from the above procedure. Moreover, it is found that the family of five LPSs have subgroup–supergroup relationships with γ-TiAl (Sp. gr. P4/mmm) and among themselves. Further, we find the inherent stability of r-Al₂Ti?+?γ-TiAl and 2Al₅Ti₃?+?γ-TiAl phase mixtures at 0?K compared to isomolecular Al₃Ti₂ and Al₁₁Ti₇ LPSs at their respective concentrations. The calculations of single-crystal elastic constants of Al₅Ti₃, Al₁₁Ti₇, Al₃Ti₂ and Al₅Ti₃′ LPSs show all these four structures are mechanically stable. We also calculate antiphase boundary (APB) formation energies for two types of APBs, viz., type-A and type-C in ordered Al₅Ti₃ LPS using the supercell approach. The relaxed APB energies for type-A and type-C APBs are 15.44 and 124.16?mJ/m², respectively.     

Electrodeposition of chitosan enables synthesis of copper/carbon composites for H2O2 sensing

This work presents a novel approach in synthesizing copper (Cu)/carbon composite materials by electrodeposition of the biopolymer chitosan, a renewable carbon precursor, on a copper anode, followed by pyrolysis of the electrodeposited chitosan gel. The amount of copper in the Cu/carbon composite material can be controlled by modifying the pH of the chitosan solution from which the electrodeposition is performed. This further influences the physical properties of the composite material. Here we show a 14 fold increase in electrical conductivity of the Cu/carbon composite, when compared to the material without copper inclusions. Metal/carbon composite materials have a wide range of applications already reported in the literature. As a proof of concept, we demonstrate the electrochemical sensing capability of this Cu/carbon material for non-enzymatic detection of hydrogen peroxide, achieving a sensitivity of 58.9 μA/mM cm², which is comparable to state of the art non-enzymatic hydrogen peroxide sensors. The anodic electrodeposition of chitosan proves to be a simple and straightforward medium for synthesis of Cu/carbon composites. We speculate that this method can be extended to obtain other metal/carbon composites as a low-cost alternative for the fabrication of functional composite electrodes.     

Synthesis of C1–C11 eribulin fragment and its diastereomeric analogues

A practical stereoselective synthesis of the central C1–C10 fragment of eribulin and its two diastereomeric analogues is developed. Our approach relied on the use of l-ascorbic acid as the starting material which allowed accessing a key intermediate with a syn diol moiety (C9 and C10 of eribulin) and a carboxylic ester group. A functionalized six membered lactone having several required hydroxyl groups was then obtained. In a number of steps, the lactone was converted to an intermediate for our key oxa-Michael reaction. A regio- and stereocontrolled intramolecular oxa-Michael reaction completed the synthesis of the C1–11 fragment having a trans-fused tetrahydropyrans with the exact stereochemistry of various hydroxyl groups, as in eribulin.     

The Effect of Corners on the Complexity of Approximate Range Searching

Given an n-element point set in ℝ ^d , the range searching problem involves preprocessing these points so that the total weight, or for our purposes the semigroup sum, of the points lying within a given query range η can be determined quickly. In ε-approximate range searching we assume that η is bounded, and the sum is required to include all the points that lie within η and may additionally include any of the points lying within distance ε⋅diam(η) of η’s boundary. In this paper we contrast the complexity of approximate range searching based on properties of the semigroup and range space. A semigroup (S,+) is idempotent if x+x=x for all x∈S, and it is integral if for all k≥2, the k-fold sum x+⋅⋅⋅+x is not equal to x. Recent research has shown that the computational complexity of approximate spherical range searching is significantly lower for idempotent semigroups than it is for integral semigroups in terms of the dependencies on ε. In this paper we consider whether these results can be generalized to other sorts of ranges. We show that, as with integrality, allowing sharp corners on ranges has an adverse effect on the complexity of the problem. In particular, we establish lower bounds on the worst-case complexity of approximate range searching in the semigroup arithmetic model for ranges consisting of d-dimensional unit hypercubes under rigid motions. We show that for arbitrary (including idempotent) semigroups and linear space, the query time is at least . In the case of integral semigroups we prove a tighter lower bound of Ω(1/ε ^d−2). These lower bounds nearly match existing upper bounds for arbitrary semigroups. In contrast, we show that the improvements offered by idempotence do apply to smooth convex ranges. We say that a range is smooth if at every boundary point there is an incident Euclidean sphere that lies entirely within the range whose radius is proportional to the range’s diameter. We show that for smooth ranges and idempotent semigroups, ε-approximate range queries can be answered in O(log n+(1/ε)^(d−1)/2log (1/ε)) time using O(n/ε) space. We show that this is nearly tight by presenting a lower bound of Ω(log n+(1/ε)^(d−1)/2). This bound is in the decision-tree model and holds irrespective of space. A preliminary version of this paper appeared in the Proc. 22nd Annu. ACM Sympos. Comput. Geom., pp. 11–20, 2006. The research of S. Arya was supported by the Research Grants Council, Hong Kong, China under project number HKUST6184/04E. The research of D.M. Mount was partially supported by the National Science Foundation under grant CCR-0635099 and the Office of Naval Research under grant N00014-08-1-1015.     

Thermo-mechanical performance of PVC/ZnO nanocomposites

The present paper deals with the study of thermo-mechanical performance of PVC/ZnO nanocomposites. The samples have been prepared by solution casting technique with different (0, 2, 4, 6 and 8) wt. % of ZnO nanoparticles in poly (vinyl chloride) (PVC) matrix and structurally characterized through scanning electron microscopy. In thermo-mechanical analysis, dynamic mechanical analyzer gives the information about storage modulus and phase transition temperature (T_g). From these viscosities, profile at elevated temperature and activation energy of phase transition can be evaluated. This study reveals that dispersion of nano-ZnO significantly altered the thermo-mechanical properties of neat PVC but the effect is composition-dependent.     

Polymer electrolytes for lithium ion batteries: a critical study

Polymer electrolytes (PEs) are an essential component being used in most energy storage/conversion devices. The present review article on a brief history, advantage, and their brief application of polymer electrolyte systems. It consists of a glimpse on liquid, gel, and solid polymer electrolyte and a contrast comparison concerning benefits/disadvantages among the three. The article started with a brief introduction of polymer electrolytes followed by their varieties and extreme uses. The role of host polymer matrix by taking numerous examples of polymer electrolyte published by the different renowned group of the concerned field has been explored. The criteria for selection of appropriate host polymer, salt, inorganic filler/clay, and aprotic solvents to be used in polymer electrolyte have been discussed in detail. The mostly used polymer, salt, solvents, and inorganic filler/clay list has been prepared in order to keep the data bank at one place for new researchers. This article comprises different methodologies for the preparation of polymer electrolyte films. The different self-proposed mechanisms (like VTF, WLF, free volume theory, dispersed/intercalated mechanisms, etc.) have been discussed in order to explain the lithium ion conduction in polymer electrolyte systems. A numerous characterization techniques and their resulting analysis have been summarized from the different published reports at one place for better awareness of the scientific community/reader of the area.     

Impact of 2OD and 3OD on SRS- and XPM-induced crosstalk in SCM-WDM optical transmission link

In this paper, the impact of second-order dispersion (2OD), third-order dispersion (3OD) and modulation frequency over stimulated Raman scattering (SRS)- and cross-phase modulation (XPM)-induced crosstalk in sub-carrier-multiplexed (SCM) wavelength division multiplexed (WDM) transmission link has been analyzed. It has been observed that there is significant effect of 2OD, 3OD and modulation frequency on the SRS- and XPM-induced crosstalk in a SCM-WDM transmission link. Here the results for SRS- and XPM-induced crosstalk have been reported with independent and combined higher-order dispersion. It has been observed that XPM-induced crosstalk lies between [−52.8 to −45.3] and [−94.7 to −78.6] dB in the presence of 2OD and 3OD respectively for modulation frequencies varied from 500 MHz to 2.0 GHz, while it is in the range of [−94.4 to −84] and [−128.5 to −117] dB when both SRS and XPM are taken into consideration.     

Optical preamplifier receiver for spectrum-sliced WDM

Spectrum-slicing provides a low-cost alternative to the use of multiple coherent lasers for wavelength division multiplexing (WDM) applications by utilizing spectral slices of a single broadband noise source for creating the multichannel system. In this paper we analyze the performance of both p-i-n and optical preamplifier receivers for spectrum-sliced WDM using actual noise distributions, and the results are compared with those using the Gaussian approximation. This extends prior results of Marcuse for the detection of deterministic signals in the presence of optical amplifier and receiver noise. Although the methodology is similar, the results are considerably different when the signal is itself noise-like. For the case of noise-like signals, it is shown that when an optical preamplifier receiver is used, there exists an optimum filter bandwidth which minimizes the detection sensitivity for a given error probability. Moreover the evaluated detection sensitivity, in photons/bit, represents an order of magnitude (>10 dB) improvement over conventional detection techniques that employ p-i-n receivers. The Gaussian approximation is shown to be overly conservative when dealing with small ratios of the receiver optical to electrical bandwidth, for both p-i-n and preamplifier receivers     

Chemistry of the natural order cupressales—41 The structure and stereochemistry of communic acid

A new diterpene acid, communic acid, has been isolated as its sodium salt from the bark of the common juniper, Juniperus communis L. The structure and configuration (1a) of this acid follows from direct correlations with torulosol and with agathene dicarboxylic acid as well as from the results of degradation experiments.