New ultrahigh affinity host-guest complexes of cucurbit[7]uril with bicyclo[2.2.2]octane and adamantane guests: thermodynamic analysis and evaluation of M2 affinity calculations

A dicationic ferrocene derivative has previously been shown to bind cucurbit[7]uril (CB[7]) in water with ultrahigh affinity (ΔG(o) = -21 kcal/mol). Here, we describe new compounds that bind aqueous CB[7] equally well, validating our prior suggestion that they, too, would be ultrahigh affinity CB[7] guests. The present guests, which are based upon either a bicyclo[2.2.2]octane or adamantane core, have no metal atoms, so these results also confirm that the remarkably high affinities of the ferrocene-based guest need not be attributed to metal-specific interactions. Because we used the M2 method to compute the affinities of several of the new host-guest systems prior to synthesizing them, the present results also provide for the first blinded evaluation of this computational method. The blinded calculations agree reasonably well with experiment and successfully reproduce the observation that the new adamantane-based guests achieve extremely high affinities, despite the fact that they position a cationic substituent at only one electronegative portal of the CB[7] host. However, there are also significant deviations from experiment, and these lead to the correction of a procedural error and an instructive evaluation of the sensitivity of the calculations to physically reasonable variations in molecular energy parameters. The new experimental and computational results presented here bear on the physical mechanisms of molecular recognition, the accuracy of the M2 method, and the usefulness of host-guest systems as test-beds for computational methods.     

OPTIMIZATION OF OXIDE-BASED ACTIVATING FLUX COMBINATION FORMULA IN ACTIVATED TUNGSTEN INERT GAS WELDING USING A HYBRID METHOD INCLUDING ARTIFICIAL NEURAL NETWORKS AND PARTICLE SWARM OPTIMIZATION

Journal of Applied Mechanics and Technical Physics - The effects of the most important process-adjusting variables (welding current and welding speed) and the percentage of the combination of...     

Immobilization of nickel ions onto the magnetic nanocomposite based on cross‐linked melamine groups: Effective heterogeneous catalyst for N‐Arylation of Arylboronic acids

A new magnetic heterogeneous catalyst was synthesized by immobilization of nickel ions onto a cross‐linked polymeric nanocomposite composed of cyanuric chloride, ethylenediamine and functionalized magnetic nanoparticles. The resulting nitrogen rich support was capable of adsorbing large amounts of nickel ions (1.20 mmol g^?1). The synthesized catalyst was characterized using AAS, TEM, FT‐IR, EDX, TGA, SEM, BET and XRD techniques. The performance of the prepared catalyst was investigated in the C‐N coupling of arylamines with aryl boronic acids. The reaction was carried out under a mild condition and good to moderate to good yields of products was obtained using only 5.0 mol% of the catalyst. The catalyst was easily recovered and reused for at least 7 times without any significant loss of its activity.     

Effect of liposome composition on β-blocker interactions studied by capillary electrokinetic chromatography

Liposome capillary electrokinetic chromatography was used to investigate the interactions between three β-blockers of different hydrophobicity and various liposome solutions. The studied β-blockers comprised alprenolol, propranolol, and carvedilol. The composition of the liposome solutions, containing 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, 1,2-dioleoyl-sn-glycero-3-phos-phoethanolamine, 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-l -serine, and cholesterol in various molar ratios, was designed by a response surface methodology-central composite design approach. Subsequently, after conducting the liposome capillary electrokinetic chromatography experiments and determining the retention factors from the electrophoretic mobilities of the compounds, and further calculating the distribution coefficients, an analysis of variance was performed. After extracting the statistical models, optimal operational conditions were obtained based on the developed models. To further investigate the interactions between the β-blockers and the liposomes, nanoplasmonic sensing experiments were carried out on two different liposome systems. The overall results demonstrate the strong influence of cholesterol and 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-l -serine on the distribution coefficients.     

Commutativity theorems for cancellative semigroups

Psomopoulos has proved that \([x^n, y] = [x, y^{n+1}]\) for a positive integer n implies commutativity in groups. Here we show that cancellative semigroups admitting commutators and satisfying the identity \([x^n, y] = [x, y^{n+k}]\) implies that the element \(y^k\) is central. The special case of \(k=1\) yields the above mentioned commutativity theorem. To accommodate negative exponents, we consider the functional equation \([f(x), y] = [x, g(y)f(y)] \) where f and g are unary functions satisfying certain formal syntactic rules and prove that in cancellative semigroups admitting commutators, the functional equation \([f(x), y] = [x, g(y)f(y)]\) implies that the element g(y) is central i.e. \(xg(y) = g(y)x\) for all x and y. By the way, these results are new even in group theory.     

Fabrication of a Nanostructure Based Electrochemical Sensor for Voltammetric Determination of Epinephrine,Uric Acid and Folic Acid

A carbon paste electrode (CPE) was modified by incorporation of graphene nano sheets and a ferrocene derivative. The modified electrode showed an excellent electrocatalytic effect on the oxidation of epinephrine. In phosphate buffer solution (PBS) of pH 7.0, the oxidation current increased linearly with concentration of epinephrine in the range of 0.05–550.0 µM and a detection limit (3σ) 27.0 nM was obtained for epinephrine. Then the modified electrode was used to determine epinephrine in an excess of uric acid and folic acid by SWV.     

Development of an in vivo radionuclide generator by labeling bleomycin with <Superscript>191</Superscript>Os

Bleomycin (BLM) has been labeled with various radioisotopes and widely used in therapy and diagnosis. ¹⁹¹Os is a parent radionuclide with 15.4 day half-life and decays by beta emission to ^191mIr, which is a radionuclide with 4.96 s half-life. BLM was labeled with ¹⁹¹Os-hexachloro-osmate and its distribution and stability in wild-type mice was determined. The complex was obtained at the pH 2 in normal saline at 90 °C in 48 h. Radio-TLC showed an overall radiochemical yield of 93–97%, radio-chemical purity > 97%. The biodistribution study for ¹⁹¹Os-hexachloro-osmate and ¹⁹¹Os-BLM were carried in wild type-mice up to 14 days. Lungs, liver and spleen uptake increased 24–72 h after administration of ¹⁹¹Os-BLM. 24 h after administration, the radioactivity of the kidney increased and remained constant.     

A contribution to the linear programming approach to joint cost allocation: Methodology and application

The linear programming (LP) approach has been commonly proposed for joint cost allocation purposes. Within a LP framework, the allocation rules are based on a marginal analysis. Unfortunately, the additivity property which is required to completely allocate joint costs fails in presence of capacity, institutional or environmental constraints.