On- and off column enantiomerization of 4,4′-bisquinolin-2-ones: A comparison of Auto-, DHPLcy2k and DCXplorer calculated thermodynamic data generated by dynamic high,performance liquid chromatography with theoretically calculated data

Fast semipreparative HPLC enantioseparation of four axially chiral biscarbostyrils (4,4′-bisquinoline-2-ones) using ULMO as a π-acidic Pirkle type chiral stationary phase leads to two racemizing pairs (1,2; k_obs 1.6 × 10⁻⁴ and 3.0 × 10⁻⁴ s⁻¹ at 28 °C) and two stable ones (3,4). 3 was stabilized by a crown ether linkage from pos. 6 to 6′, and 4 had sterically demanding bromo substituents in pos. 3 and 3′. On-column generated temperature-dependent chromatograms of 1 and 2 were fitted with Auto-DHPLCy2k and DCXplorer. For cpd 2 both programs delivered similar ΔG values of 90 and 93 kJ/mol, well comparable with the 99 kJ/mol calculated with the B3LYP/6-31G (d) procedure. At temperatures of high conversion DCXplorer delivered inconsistent series of rate constants for the more tailing and less resolved tetramethoxy derivative 1. We connect this problem with an almost impossible halfwidth calculation of tailing peak pairs which are weakly resolved. However, this problem could be observed only in the case of tetramethoxy derivative 1. Stochastic generated data of Auto-DHPLCy2k could be used at a lower percentage of conversion only while the theoretical plate model did not deliver useful data at temperatures of very low conversion but fitted well high conversion chromatogram series of 1 and 2.     

Convenient Ultrasound-Promoted Regioselective Synthesis of Fused 6-Amino-3-methyl-4-aryl-1H-pyrazolo[3,4-b]pyridine-5-carbonitrile

A multicomponent, catalyst-free reaction for the synthesis of fused 6-amino-3-methyl-4-aryl-1H-pyrazolo [3,4-b] pyridine-5-carbonitrile from 3-amino-5-methylpyrazole, malononitrile, and substituted aldehydes under ultrasound irradiation in short reaction times (8–10 min) with good yields (85–98%) is reported.

Toward design and fabrication of wind-driven vehicles: Procedure to optimize the threshold of driving forces

Wind energy has been continuously considered as a green, available, and economical alternative source of energy. For centuries, the transformed wind energy to drag-force has been used for transportation in watercrafts. With improvement of aerodynamics, the airfoil was invented to create and use a higher magnitude aerodynamic force, lift-force, in order to elevate airplanes. Later, the lift-force was horizontally applied as the thrust force in land/water wind-crafts. Whereas in airplanes horizontal airfoils (wing) create a vertical lift-force, installed vertical airfoils (wing-sail) produce a horizontal lift-force in wind-crafts. Therefore, this force can be used as thrust (driving) force in lift-based ice, water, and land vehicles. If the prevailing wind is constantly available, the vehicle speed can even exceed the wind velocity. Due to the complex kinematics of such vehicles, however, it should be noted that there would be always an optimum for the thrust force in order to control and navigate the vehicle to the destination point, and to avoid the severe undesired side-forces. This optimum is calculated in wind-craft trajectory software (WTS) which requires many inputs, including variable and constant parameters. Variable parameters consist of wind direction and magnitude in addition to vehicle’s position, velocities, and accelerations. On the other hand, design characteristics of the wind-driven vehicle are known as constant parameters. The land-yacht body’s drag is an unknown constant parameter which alters according to the relative wind. This implies that several wind tunnel experiment in different wind directions and speeds are required in order to obtain the drag coefficients.Therefore in order to bypass the wind tunnel measurements, this study aims to propose a fast and economical procedure to find the aforementioned drag coefficient by integration of a measurement and by a simulation approach. The obtained data can be later used in the optimization and control module of the WTS. The performance of this procedure has been investigated using a case study. For this purpose, a 1:4 prototype three-wheel land-yacht is first designed and fabricated. The land-yacht comprises of three major parts; horizontal airfoil (axle), vertical airfoil, and body. The dimensions of these elements are obtained after development of a code based on kinematics of the land-yacht. The axle is designed to increase the stability of the land-yacht, whereas the shape of the body is intended to produce a low drag coefficient in various directions. Furthermore, a set of experiments has been conducted to measure the body drag of the land-yacht in a direction parallel to the relative wind. This experiment is later used to develop and validate a computational fluid dynamics (CFD) model in order to estimate the drag of the land-yacht body in its various directions against the relative wind. The results show the adequate efficacy of this procedure to provide the required data for the optimization and control module of the WTS.     

Design and synthesis of novel polyglycerol hybrid nanomaterials for potential applications in drug delivery systems

The synthesis of a new drug delivery system based on hybrid nanomaterials containing a β-CD core and hyperbranched PG is described. Conjugating PG branches onto β-CD not only increases its water solubility but also affects its host/guest properties deeply. It can form molecular inclusion complexes with small hydrophobic guest molecules such as ferrocene or FITC with reasonable release. In addition, the achievable payloads are significantly higher as for carriers such as hyperbranched PGs. Short-term in vitro cytotoxicity and hemocompatibility tests on L929 cell lines show that the hybrid nanomaterial is highly biocompatible. Due to their outstanding properties, β-CD-g-PG hybrid nanomaterials are introduced as promising materials for nanomedicine, e.g., for drug delivery issues.     

A simple Schiff base as selective and sensitive fluorescent-colorimetric hydrazine chemosensor

ABSTRACT

A new fluorescent-colorimetric chemosensor L has been synthesised by Schiff base condensation reaction between 1,8-diaminooctane and 4-nitro-benzaldehyde in very good yields. Its photo-luminescent properties and selective detection properties for hydrazine have been examined. The synthesised chemosensor exhibited highly selective fluorescence on-off response for hydrazine amongst a wide range of different metal cations, anions and amines, along with the bare eye colour change from colourless to yellow based on intermolecular hydrogen-bond interaction. The limit of detection of the chemosensor L was estimated as 9.77 × 10^?8 M or 3.12 × 10^?6 g L^?1 for hydrazine which is extremely below the limit set by the World Health Organization (WHO) and the binding stoichiometry was proposed to be 1 : 2 based on ¹H NMR spectroscopic techniques and the Job’s plot analysis. The proposed sensing mechanism is the hydrogen-bonding interaction which has further been established by Density Functional Theory (Functional Density Theory (DFT)) studies. This recognition feature of sensor L makes it an efficient chemosensor for hydrazine detection in different water samples.     

Evaluating the Synthesis of Bis‐pyrazolines

The bis‐cyclization of chalcone with thiosemicarbazide under basic condition led to the formation of new compounds, thiocarbamoyl bis‐pyrazoline derivatives. Bis‐chalcones were prepared by a Claisen–Schmidt condensation between 1 mol bis‐aldehyde and 2 mol acetophenone derivatives in the presence of sodium hydroxide as a catalyst. The structures of all compounds were elucidated by IR, ¹H NMR, and ¹³C NMR spectral data and by elemental analyses.     

Bilipschitz homogeneous Jordan curves

We characterize bilipschitz homogeneous Jordan curves by utilizing quasihomogeneous parameterizations. We verify that rectifiable bilipschitz homogeneous Jordan curves satisfy a chordarc condition. We exhibit numerous examples including a bilipschitz homogeneous quasicircle which has lower Hausdorff density zero. We examine homeomorphisms between Jordan curves.

     

New bounds for the chromatic number of graphs

In this article we first give an upper bound for the chromatic number of a graph in terms of its degrees. This bound generalizes and modifies the bound given in 11 . Next, we obtain an upper bound of the order of magnitude for the coloring number of a graph with small K_2,t (as subgraph), where n is the order of the graph. Finally, we give some bounds for chromatic number in terms of girth and book size. These bounds improve the best known bound, in terms of order and girth, for the chromatic number of a graph when its girth is an even integer. © 2008 Wiley Periodicals, Inc. J Graph Theory 58:110–122, 2008     

HAp‐encapsulated γ‐Fe2O3‐supported dual acidic heterogeneous catalyst for highly efficient one‐pot synthesis of benzoxanthenones and 3‐pyranylindoles

A novel method is reported for the synthesis of benzoxanthenone and 3‐pyranylindole derivatives via one‐pot three‐component reactions using a newly synthesized HAp‐encapsulated γ‐Fe₂O₃‐supported dual acidic heterogeneous catalyst, as a reusable and highly efficient nanocatalyst. In this protocol the use of the nanocatalyst provided a green, useful and rapid method to generate products in short reaction times (4–20 min) and in excellent yields (87–96%). The paramagnetic nature of the catalyst provided a simple, trouble‐free and facile approach for the separation of the catalyst by applying an external magnet, and it could be used in eight cycles without significant loss in catalytic efficiency.