Peak effect studies in single crystals CeRu2 and 2H-NbS2

We have studied the peak effect (PE) phenomenon in single crystals of weakly pinned superconductors CeRu₂ and 2H-NbS₂. 2H-NbS₂ is iso-structural and iso-electronic to 2H-NbSe₂, whose similarity with CeRu₂ as regards the PE representing the order-to-disorder transformation of the flux line lattice was claimed some time ago. We report on the step change in equilibrium magnetization across the peak effect in CeRu₂. We also present the vortex phase diagram of 2H-NbS₂ obtained from the magnetization data, and compare the PE phenomenon in 2H-NbS₂ and 2H-NbSe₂.     

Parallel asynchronous focal plane array processing

A new approach to focal plane processing based on silicon injection mode devices is suggested. These devices provide a natural basis for parallel asynchronous focal plane image preprocessing. The simplicity and novel properties of the devices would permit an independent analog processing channel to be dedicated to every pixel. A laminar architecture built from arrays of the devices would form a two-dimensional (2-D) array processor with a 2-D array of inputs located directly behind the focal plane detector array. A 2-D image data stream would propagate in neuronlike asynchronous pulse coded form through the laminar processor. No multiplexing, digitization or serial processing would occur in the preprocessing stage. High performance is expected because approximately linear pulse coding has already been observed for input currents ranging over six orders of magnitude down to one picoampere with noise referred to input of about 10 femtoamperes. Very low power requirements suggest utility in space and in conjunction with very large arrays. Multispectral processing is possible because of compatibility with the cryogenic environment of high performance infrared detectors.     

Boronate affinity saccharide electrophoresis: a novel carbohydrate analysis tool

The incorporation of specialised carbohydrate affinity ligand methacrylamido phenylboronic acid in polyacrylamide gels for fluorophore-assisted carbohydrate electrophoresis greatly improved the effective separation of saccharides that show similar mobilities in standard electrophoresis. Polyacrylamide gel electrophoresis using methacrylamido phenylboronic acid in low loading (typically 0.5-1% dry weight) was unequivocally shown to alter retention of labelled saccharides depending on their boronate affinity. While conventional fluorophore-assisted carbohydrate electrophoresis of 2-aminoacridone labelled glucose oligomers showed an inverted parabolic migration, an undesired trait of small oligosaccharides labelled with this neutral fluorophore, boron affinity saccharide electrophoresis separation of these carbohydrates completely restored their predicted running order, based on their charge/mass ratio, and resulted in improved separation of the analyte saccharides. These results exemplify boron affinity saccharide electrophoresis as an important new technique for analysing carbohydrates and sugar-containing molecules.     

Highly Flexible Dielectric Films from Solution Processable Covalent Organic Frameworks**

Covalent organic frameworks (COFs) are known to be a promising class of materials for a wide range of applications, yet their poor solution processability limits their utility in many areas. Here we report a pore engineering method using hydrophilic side chains to improve the processability of hydrazone and β-ketoenamine-linked COFs and the production of flexible, crystalline films. Mechanical measurements of the free-standing COF films of COF-PEO-3 (hydrazone-linked) and TFP-PEO-3 (β-ketoenamine-linked), revealed a Young's modulus of 391.7 MPa and 1034.7 MPa, respectively. The solubility and excellent mechanical properties enabled the use of these COFs in dielectric devices. Specifically, the TFP-PEO-3 film-based dielectric capacitors display simultaneously high dielectric constant and breakdown strength, resulting in a discharged energy density of 11.22 J cm⁻³. This work offers a general approach for producing solution processable COFs and mechanically flexible COF-based films, which hold great potential for use in energy storage and flexible electronics applications.     

Parallel implementation of electronic structure energy, gradient, and Hessian calculations

ACES III is a newly written program in which the computationally demanding components of the computational chemistry code ACES II [J. F. Stanton et al., Int. J. Quantum Chem. 526, 879 (1992); [ACES II program system, University of Florida, 1994] have been redesigned and implemented in parallel. The high-level algorithms include Hartree-Fock (HF) self-consistent field (SCF), second-order many-body perturbation theory [MBPT(2)] energy, gradient, and Hessian, and coupled cluster singles, doubles, and perturbative triples [CCSD(T)] energy and gradient. For SCF, MBPT(2), and CCSD(T), both restricted HF and unrestricted HF reference wave functions are available. For MBPT(2) gradients and Hessians, a restricted open-shell HF reference is also supported. The methods are programed in a special language designed for the parallelization project. The language is called super instruction assembly language (SIAL). The design uses an extreme form of object-oriented programing. All compute intensive operations, such as tensor contractions and diagonalizations, all communication operations, and all input-output operations are handled by a parallel program written in C and FORTRAN 77. This parallel program, called the super instruction processor (SIP), interprets and executes the SIAL program. By separating the algorithmic complexity (in SIAL) from the complexities of execution on computer hardware (in SIP), a software system is created that allows for very effective optimization and tuning on different hardware architectures with quite manageable effort.     

Approaches toward the Separation,Modification, Identification and Scale up Purification of Tetracyclic Diterpene Glycosides from Stevia rebaudiana (Bertoni) Bertoni

Stevia rebaudiana (Bertoni) Bertoni is a plant species native to Brazil and Paraguay well-known by the sweet taste of their leaves. Since the recognition of rebaudioside A and other steviol glycosides as generally recognized as safe by the United States Food and Drug Administration in 2008 and grant of marketing approval by the European Union in 2011, the species has been widely cultivated and studied in several countries. Several efforts have been dedicated to the isolation and structure elucidation of minor components searching for novel non-caloric sugar substitutes with improved organoleptic properties. The present review provides an overview of the main chemical approaches found in the literature for identification and structural differentiation of diterpene glycosides from Stevia rebaudiana: High-performance Thin-Layer Chromatography, High-Performance Liquid Chromatography, Electrospray Ionization Mass Spectrometry and Nuclear Magnetic Resonance Spectroscopy. Modification of diterpene glycosides by chemical and enzymatic reactions together with some strategies to scale up of the purification process saving costs are also discussed. A list of natural diterpene glycosides, some examples of chemically modified and of enzymatically modified diterpene glycosides reported from 1931 to February 2021 were compiled using the scientific databases Google Scholar, ScienceDirect and PubMed.     

Recasting the Elliott conjecture

Let A be a simple, unital, finite, and exact C^*-algebra which absorbs the Jiang–Su algebra tensorially. We prove that the Cuntz semigroup of A admits a complete order embedding into an ordered semigroup which is obtained from the Elliott invariant in a functorial manner. We conjecture that this embedding is an isomorphism, and prove the conjecture in several cases. In these same cases— -stable algebras all—we prove that the Elliott conjecture in its strongest form is equivalent to a conjecture which appears much weaker. Outside the class of -stable C^*-algebras, this weaker conjecture has no known counterexamples, and it is plausible that none exist. Thus, we reconcile the still intact principle of Elliott’s classification conjecture—that -theoretic invariants will classify separable and nuclear C^*-algebras—with the recent appearance of counterexamples to its strongest concrete form. Research supported by the DGI MEC-FEDER through Project MTM2005-00934, and the Comissionat per Universitats i Recerca de la Generalitat de Catalunya. A. S. Toms was also supported in part by an NSERC Discovery Grant.     

Towards a more accurate reference interaction site model integral equation theory for molecular liquids

A systematic approach for increasing the accuracy of the reference interaction site model (RISM) theory is introduced that uses input from simulation results to produce very accurate site-site pair correlation functions for single component molecular liquids. The methodology allows the computation of the "RISM bridge function." Realistic molecular liquids such as water, alcohols, amides, and others are investigated, and the merits and limitations of the method for each of these liquids are examined in relation to the known deficiencies of the RISM theory.     

Gas-phase fragmentation of deprotonated p-hydroxyphenacyl derivatives

Electrospray ionization of methanolic solutions of p-hydroxyphenacyl derivatives HO-C(6)H(4)-C(O)-CH(2)-X (X = leaving group) provides abundant signals for the deprotonated species which are assigned to the corresponding phenolate anions (-)O-C(6)H(4)-C(O)-CH(2)-X. Upon collisional activation in the gas phase, these anions inter alia undergo loss of a neutral "C(8)H(6)O(2)" species concomitant with formation of the corresponding anions X(-). The energies required for the loss of the neutral roughly correlate with the gas phase acidities of the conjugate acids (HX). Extensive theoretical studies performed for X = CF(3)COO in order to reveal the energetically most favorable pathway for the formation of neutral "C(8)H(6)O(2)" suggest three different routes of similar energy demands, involving a spirocyclopropanone, epoxide formation, and a diradical, respectively.     

Sterically congested, hexameric tetrakispyridinyl-Pd(II)/Cd(II)-metallomacrocycles: self-assembly and structural characterization

Hexagonal Pd(II)- or Cd(II)-tetrakispyridinyl-based macrocycles are quantitatively self-assembled from 4'-(3-pyridinyl)-4,4'-di(tert-butyl)-2,2'?:?6',2'-terpyridine and structurally confirmed by NMR and TWIM-MS.