Synthesis,crystal structure and spectroscopic studies of 3-hydrazono- and 3-hydroxyiminoquinolin-2-ones

3-(Hydrazonoethyl)quinolinones 6–11, 13 and 3-(hydroxyiminoethyl)quinolinones 14, 15 are prepared by a condensation reaction of 3-acetylquinolinones 4, 5 with a variety of 1,2-(bis)nucleophiles. The structures of the isolated compounds have been elucidated using ¹H and ¹³C nmr spectroscopy. X-ray diffraction studies of compound 14 were also performed.     

Pore Network Analysis of Resistivity Index for Water-Wet Porous Media

Pore network analysis is used to investigate the effects of microscopic parameters of the pore structure such as pore geometry, pore-size distribution, pore space topology and fractal roughness porosity on resistivity index curves of strongly water-wet porous media. The pore structure is represented by a three-dimensional network of lamellar capillary tubes with fractal roughness features along their pore-walls. Oil-water drainage (conventional porous plate method) is simulated with a bond percolation-and-fractal roughness model without trapping of wetting fluid. The resistivity index, saturation exponent and capillary pressure are expressed as approximate functions of the pore network parameters by adopting some simplifying assumptions and using effective medium approximation, universal scaling laws of percolation theory and fractal geometry. Some new phenomenological models of resistivity index curves of porous media are derived. Finally, the eventual changes of resistivity index caused by the permanent entrapment of wetting fluid in the pore network are also studied.Resistivity index and saturation exponent are decreasing functions of the degree of correlation between pore volume and pore size as well as the width of the pore size distribution, whereas they are independent on the mean pore size. At low water saturations, the saturation exponent decreases or increases for pore systems of low or high fractal roughness porosity respectively, and obtains finite values only when the wetting fluid is not trapped in the pore network. The dependence of saturation exponent on water saturation weakens for strong correlation between pore volume and pore size, high network connectivity, medium pore-wall roughness porosity and medium width of the pore size distribution. The resistivity index can be described succesfully by generalized 3-parameter power functions of water saturation where the parameter values are related closely with the geometrical, topological and fractal properties of the pore structure.     

Warfarin Sodium Stability in Oral Formulations

Warfarin sodium is a low-dose pharmaceutical blood thinner that exists in two forms: the clathrate form and the amorphous form. In commercially available warfarin sodium oral suspension, the active pharmaceutical ingredient (API) is added in the amorphous state. This study investigates the apparent instability of the commercially available warfarin liquid oral formulation using Raman and IR spectroscopy, X-ray diffraction, differential scanning calorimetry, UV spectroscopy, and optical microscopy. Warfarin, not its sodium salt, was identified as the undissolved solid existing in the suspension. This was found to be due to the dissociation of sodium salt and the protonation of the warfarin ion in the liquid phase, which triggered the crystallization of the sparingly soluble unsalted form. The coexistence of protonated and unprotonated warfarin ions in the supernatant, as detected by Raman and UV spectroscopy, confirmed this assumption. Study of the dissolution of warfarin sodium amorphous salt and crystalline sodium clathrate in the placebo and pure water verified the results. The effect of pH and temperature on warfarin precipitation was also explored.     

The surprising pairing of 2‐aminoimidazo[1,2‐a][1,3,5]triazin‐4‐one,a component of an expanded DNA alphabet

Synthetic biologists demonstrate their command over natural biology by reproducing the behaviors of natural living systems on synthetic biomolecular platforms. For nucleic acids, this is being done stepwise, first by adding replicable nucleotides to DNA, and then removing its standard nucleotides. This challenge has been met in vitro with `six‐letter' DNA and RNA, where the Watson–Crick pairing `concept' is recruited to increase the number of independently replicable nucleotides from four to six. The two nucleobases most successfully added so far are Z and P , which present a donor–donor–acceptor and an acceptor–acceptor–donor pattern, respectively. This pair of nucleobases are part of an `artificially expanded genetic information system' (AEGIS). The Z nucleobase has been already crystallized, characterized, and published in this journal [Matsuura et al. (2016). Acta Cryst. C 72 , 952–959]. More recently, variants of Taq polymerase have been crystallized with the pair P : Z trapped in the active site. Here we report the crystal structure of the nucleobase 2‐aminoimidazo[1,2‐a][1,3,5]triazin‐4‐one (trivially named P ) as the monohydrate, C₅H₅N₅O·H₂O. The nucleobase P was crystallized from water and characterized by X‐ray diffraction. Interestingly, the crystal structure shows two tautomers of P packed in a Watson–Crick fashion that cocrystallized in a 1:1 ratio.     

Acid‐Catalyzed Cyclization of Terpenes Under Homogeneous and Heterogeneous Conditions as Probed Through Stereoisotopic Studies: A Concerted Process with Competing Preorganized Chair and Boat Transition States

Based on stereoisotopic studies and β‐secondary isotope effects, we propose that the acid‐catalyzed cyclization of geranyl acetate proceeds through a concerted mechanism. Under heterogeneous conditions (zeolite Y confinement), a preorganized chairlike transition state predominates, whereas under homogeneous conditions the boat‐ and chairlike transition states are almost isoenergetic. For the case of farnesyl acetate, we propose that under homogeneous conditions a concerted dicyclization occurs with a preorganized boat–chair transition state competing with the chair–chair transition state. Under zeolite confinement conditions, the chair–chairlike dicyclization transition state is highly favorable. The preference of chairlike transition states within the cavities of zeolite Y is attributed to a transition state shape selectivity effect.     

Hetero-heptanuclear (Fe–Na) complexes of salicylaldehydes: crystal and molecular structure of [Fe2(3-OCH3-salo)8 · Νa5] · 3OH · 8H2Ο

The reaction of Fe(III) with the substituted salicylaldehydes [X-saloH, where X = 3-OCH₃ (L ¹ ), 5-CH₃ (L ² ), 5-Cl (L ³ ), 5-NO₂ (L ⁴ )] led to the formation of four new iron(III) hetero-heptanuclear complexes (Fe–Na) under the general formula [Fe₂(X-salo)₈Νa₅] · 3OH · zH₂Ο. The two different coordination modes of the ligand, as well as the geometry around the metal ions were deduced by X-ray structure analysis of compound 1, [Fe₂(3-OCH₃-salo)₈Νa₅] · 3OH · 8H₂Ο. The complexes have also been characterized by physicochemical and spectroscopic (IR, UV–Vis, Mössbauer) methods.     

Capillary waveguide fluoroimmunosensor with improved repeatability and detection sensitivity

An optical capillary waveguide fluoroimmunosensor based on glass capillaries internally coated with an ultrathin poly(dimethylsiloxane) (PDMS) film is presented. The evaluation of the capillaries developed was done in comparison with aminosilanized [3-(aminopropyl)triethoxysilane, APTES] glass and poly(methylpentene) (PMP) capillaries by immobilizing rabbit γ-globulins on the internal capillary wall. Following reaction with (R)-phycoerythrin-labelled antibody, the capillary was scanned with a laser beam and the fluorescence waveguided through the capillary wall was detected by a photomultiplier placed at one of its ends. The capillaries developed provided considerably improved protein coating homogeneity (intracapillary coefficients of variation 2.9–6.6%) and repeatability (intercapillary coefficients of variation 2.1–5.0%) compared with APTES-treated ones (7.9–13.4 and 8.5–15.2%, respectively). With use of these capillaries in a sandwich-type immunosensor for the determination of rabbit γ-globulins, the assay detection limit was improved eightfold (4.4 ng/mL) compared with that obtained using PMP capillaries (35.3 ng/mL), whereas the assay repeatability was improved threefold (intra-assay coefficients of variation 5.9–13.1%) compared with APTES-treated capillaries (15.6–36%). Optoelectronic set-up used to scan the capillaries (left) and representative fluorescence scannings of dual-band poly(methylpentene) (PMP), PDMS-modified glass and APTES treated glass capillaries     

Weighing Matrices and String Sorting

In this paper we establish a fundamental link between the search for weighing matrices constructed from two circulants and the operation of sorting strings, an operation that has been studied extensively in computer science. In particular, we demonstrate that the search for weighing matrices constructed from two circulants using the power spectral density criterion and exploiting structural patterns for the locations of the zeros in candidate solutions, can be viewed as a string sorting problem together with a linear time algorithm to locate common strings in two sorted arrays. This allows us to bring into bear efficient algorithms from the string sorting literature. We also state and prove some new enhancements to the power spectral density criterion, that allow us to treat successfully the rounding error effect and speed up the algorithm. Finally, we use these ideas to find new weighing matrices of order 2n and weights 2n – 13, 2n – 17 constructed from two circulants.     

A Guided Tabu Search for the Vehicle Routing Problem with two-dimensional loading constraints

We present a metaheuristic methodology for the Capacitated Vehicle Routing Problem with two-dimensional loading constraints (2L-CVRP). 2L-CVRP is a generalisation of the Capacitated Vehicle Routing Problem, in which customer demand is formed by a set of two-dimensional, rectangular, weighted items. The purpose of this problem is to produce the minimum cost routes, starting and terminating at a central depot, to satisfy the customer demand. Furthermore, the transported items must be feasibly packed into the loading surfaces of the vehicles. We propose a metaheuristic algorithm which incorporates the rationale of Tabu Search and Guided Local Search. The loading aspects of the problem are tackled using a collection of packing heuristics. To accelerate the search process, we reduce the neighbourhoods explored, and employ a memory structure to record the loading feasibility information. Extensive experiments were conducted to calibrate the algorithmic parameters. The effectiveness of the proposed metaheuristic algorithm was tested on benchmark instances and led to several new best solutions.