Growth and characterization of a novel organic nonlinear optical material: l-alanine 2-furoic acid

l-alanine 2-furoic acid (LA2FA), a novel organic third order nonlinear optical material was grown by slow solvent evaporation technique at room temperature. The grown single crystals were characterized by XRD, spectral, thermal, optical, dielectric and third order nonlinear properties. LA2FA crystallizes into triclinic system with the space group P1. The cell parameters are found to be a = 3.97 Å, b = 7.09 Å, c = 10.69 Å, α = 73.61°, β = 83.57°, γ = 84.21° and V = 286 Å3. The modes of vibrations of different molecular groups present in LA2FA were identified by FTIR studies. The optical transparency of the grown crystals was investigated by UV–visible spectrum. The absorption spectrum reveals that the crystal has a high UV cut off of 245 nm and photonic band gap of 2.5 eV. The scanning electron microscope (SEM) study has been carried out to determine the surface morphology of the grown crystal. The thermal behavior of the crystal investigated using thermo gravimetric (TG) and differential thermal analysis (DTA) indicates that the material does not decompose before melting. The third order NLO property was studied in detail by z-scan technique.     

Uncommon hydrogen bonds between a non-classical ethyl cation and π hydrocarbons: a preliminary study

This study undertakes a theoretical investigation into uncommon hydrogen bonds between the ethyl cation (C₂H₅ ⁺) and π hydrocarbons. Firstly, it considers the hyperconjugation effect of the ethyl cation, in which the non-localized hydrogen (H⁺) is taken to be a pseudoatom bound to the carbons of the methyl groups. The goal of the research is to use this electronic phenomenon to gain a better understanding of the (H⁺···π) and (H⁺···p-π) hydrogen bonds, which are considered uncommon because they are formed through the interaction of the H⁺ of the ethyl cation with the π bonds of the acetylene (C₂H₂) and ethene (C₂H₄), as well as with the pseudo-π bond of the cyclopropane (C₃H₆). In view of this, B3LYP/6-311++G(d,p) calculations were used to determine the geometries of the C₂H₅ ⁺···C₂H₂, C₂H₅ ⁺···C₂H₄, and C₂H₅ ⁺···C₃H₆ hydrogen-bonded complexes. Deformations of the bond lengths and bond angles of these systems were analyzed geometrically. Examination of the stretch frequencies and absorption intensities of the (H⁺···π) and (H⁺···p-π) hydrogen bonds has revealed red-shifts in π and p-π bonds. After structural modeling and vibrational characterization, analysis of the charge transfer following the ChelpG approach and subsequently quantification of the hydrogen bond energies (basis sets superpostition error and zero point vibrational energies being considered) were used to predict the strength of the (H⁺···π) and (H⁺···p-π) hydrogen bonds. In addition, the molecular topography was estimated using the quantum theory of atoms in molecules (QTAIM). QTAIM was chosen because of a desire to understand the (H⁺···π) and (H⁺···p-π) hydrogen bonds chemically on the basis of the quantity of charge density and interpretation of Laplacian fields. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Superfilters, Ramsey theory, and van der Waerden's Theorem

Superfilters are generalizations of ultrafilters, and capture the underlying concept in Ramsey-theoretic theorems such as van der Waerden's Theorem. We establish several properties of superfilters, which generalize both Ramsey's Theorem and its variants for ultrafilters on the natural numbers. We use them to confirm a conjecture of Kočinac and Di Maio, which is a generalization of a Ramsey-theoretic result of Scheepers, concerning selections from open covers. Following Bergelson and Hindman's 1989 Theorem, we present a new simultaneous generalization of the theorems of Ramsey, van der Waerden, Schur, Folkman–Rado–Sanders, Rado, and others, where the colored sets can be much smaller than the full set of natural numbers.     

Setting gates for activities in the stochastic project scheduling problem through the cross entropy methodology

This paper addresses the problem of scheduling activities in projects with stochastic activity durations. The aim is to determine for each activity a gate—a time before it the activity cannot begin. Setting these gates is analogous to setting inventory levels in the news vendor problem. The resources required for each activity are scheduled to arrive according to its gate. Since activities’ durations are stochastic, the start and finish time of each activity is uncertain. This fact may lead to one of two outcomes: (1) an activity is ready to start its processing as all its predecessors have finished, but it cannot start because the resources required for it were scheduled to arrive at a later time. (2) The resources required for the activity have arrived and are ready to be used but the activity is not ready to start because of precedence constraints. In the first case we will incur a “holding” cost while in the second case, we will incur a “shortage” cost. Our objective is to set gates so as to minimize the sum of the expected holding and shortage costs. We employ the Cross-Entropy method to solve the problem. The paper describes the implementation of the method, compares its results to various heuristic methods and provides some insights towards actual applications.     

Nature plays with dice – terrorists do not: Allocating resources to counter strategic versus probabilistic risks

Probabilistic uncertainty is caused by “chance”, whereas strategic uncertainty is caused by an adverse interested party. Using linear impact functions, the problems of allocating a limited resource to defend sites that face either probabilistic risk or strategic risk are formulated as optimization problems that are solved explicitly. The resulting optimal policies differ – under probabilistic risk, the optimal policy is to focus the investment of resources on priority sites where they yield the highest impact, while under strategic risk, the best policy is to spread the resources so as to decrease the potential damage level of the most vulnerable site(s). Neither solution coincides with the commonly practiced proportionality allocation scheme.     

Enzyme assays with boronic acid appended bipyridinium salts

In-vitro fluorescent enzyme assays have been developed for sucrose phosphorylase (SPO) and phosphoglucomutase (PGM). These assays make use of a selective carbohydrate sensing system that detects the unlabeled enzymatic products fructose and glucose-6-phosphate. The system comprises 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt as the reporter unit and boronic acid appended viologens as selective receptors with working ranges from 70 μM to 1.0 mM for fructose (SPO) and 190 μM to 2.0 mM for glucose-6-phosphate (PGM). The change in fluorescence can be converted into product concentration, allowing initial reaction velocities and Michaelis-Menten kinetics to be calculated. The assays are also carried out in multiwell plate formats, making them suitable for high-throughput screening of enzyme inhibitors. Rapid PGM inhibition screening is demonstrated with EDTA and LiCl. The PGM assay can also be used for enzyme quantification with a detection limit of 50 ng mL⁻¹.     

Voltage-controlled metal binding on polyelectrolyte-functionalized nanopores

Most of the research in the field of nanopore-based platforms is focused on monitoring ion currents and forces as individual molecules translocate through the nanopore. Molecular gating, however, can occur when target analytes interact with receptors appended to the nanopore surface. Here we show that a solid state nanopore functionalized with polyelectrolytes can reversibly bind metal ions, resulting in a reversible, real-time signal that is concentration dependent. Functionalization of the sensor is based on electrostatic interactions, requires no covalent bond formation, and can be monitored in real time. Furthermore, we demonstrate how the applied voltage can be employed to tune the binding properties of the sensor. The sensor has wide-ranging applications and, its simplest incarnation can be used to study binding thermodynamics using purely electrical measurements with no need for labeling.