An improved spectral homotopy analysis method for MHD flow in a semi-porous channel

In this paper we report on a novel method for solving systems of highly nonlinear differential equations by blending two recent semi-numerical techniques; the spectral homotopy analysis method and the successive linearisation method. The hybrid method converges rapidly and is an enhancement of the utility of the original spectral homotopy analysis method (Motsa et al., Commun Nonlinear Sci Numer Simul 15:2293?C2302, 2010; Computer & Fluids 39:1219?C1225, 2010) and an improvement on other recent semi-analytical techniques. We illustrate the application of the method by solving a system of nonlinear differential equations that govern the problem of laminar viscous flow in a semi-porous channel subject to a transverse magnetic field. A comparison with the numerical solution confirms the validity and accuracy of the technique and shows that the method converges rapidly and gives very accurate results.     

Reactions of bis(tetrazole)phenylenes. Surprising formation of vinyl compounds from alkyl halides

The reactions of 1,2-bis(tetrazol-5-yl)benzene (1), 1,3-bis(tetrazol-5-yl)benzene (2), 1,4-bis(tetrazol-5-yl)benzene (3), 1,2-(Bu₃SnN₄C)₂C₆H₄ (4), 1,3-(Bu₃SnN₄C)₂C₆H₄ (5) and 1,4-(Bu₃SnN₄C)₂C₆H₄ (6) with 1,2-dibromoethane were carried out by two different methods in order to synthesise pendant alkyl halide derivatives of the parent bis-tetrazoles. This lead to the formation of several alkyl halide derivatives, substituted at either N1 or N2 on the tetrazole ring, as well as the surprising formation of several vinyl derivatives. The crystal structures of both 1,2-[(2-vinyl)tetrazol-5-yl)]benzene (1-N,2-N′) (1b) and 1,3-bis[(2-bromoethyl)tetrazol-5-yl]benzene (2-N,2-N′) (5d) are discussed.     

Cyclic nitriles: diastereoselective alkylations

[reaction: see text] Diastereoselective alkylations of metalated conformationally locked 4-tert-butylcyclohexanecarbonitrile are highly diastereoselective with magnesium and copper counterions but only modestly diastereoselective with lithium as the counterion. Selective generation of diverse metalated nitriles is readily achieved through bromine-magnesium, -copper, and -lithium exchange reactions of the corresponding bromonitrile or, for lithium, by deprotonating the parent nitrile with lithium diethylamide. Collectively, high alkylation stereoselectivities correlate with the retentive alkylations of C-metalated nitriles, whereas N-lithiated nitriles alkylate with modest selectivity, reflecting minimal steric differences in the corresponding axial and equatorial electrophile trajectories.     

Ultrafast fluorescence depolarisation in the yellow fluorescent protein due to its dimerisation.

Transient absorption spectroscopy with sub-100 fs time resolution was performed to investigate the oligomerisation behaviour of eYFP in solution. A single time constant tau(AD)=2.2+/-0.15 ps is sufficient to describe the time-resolved anisotropy decay up to at least 200 ps. The close contact of two protein barrels is deduced as the exclusive aggregation state in solution. From the final anisotropy r(infinity)=0.28+/-0.02, the underlying quaternary structure can be traced back to the somewhat distorted structure of the dimers of wt-GFP. The use of autofluorescent proteins as rulers in F?rster resonance energy transfer (FRET) measurements may demand polarisation-sensitive detection of the fluorescence with high time resolution.     

Small Molecule Fisetin Modulates Alpha–Synuclein Aggregation

Phenolic compounds are thought to be important to prevent neurodegenerative diseases (ND). Parkinson’s Disease (PD) is a neurodegenerative disorder known for its typical motor features, the deposition of α-synuclein (αsyn)-positive inclusions in the brain, and for concomitant cellular pathologies that include oxidative stress and neuroinflammation. Neuroprotective activity of fisetin, a dietary flavonoid, was evaluated against main hallmarks of PD in relevant cellular models. At physiologically relevant concentrations, fisetin protected SH-SY5Y cells against oxidative stress overtaken by tert-butyl hydroperoxide (t-BHP) and against methyl-4-phenylpyridinuim (MPP⁺)-induced toxicity in dopaminergic neurons, the differentiated Lund human Mesencephalic (LUHMES) cells. In this cellular model, fisetin promotes the increase of the levels of dopamine transporter. Remarkably, fisetin reduced the percentage of cells containing αsyn inclusions as well as their size and subcellular localization in a yeast model of αsyn aggregation. Overall, our data show that fisetin exerts modulatory activities toward common cellular pathologies present in PD; remarkably, it modulates αsyn aggregation, supporting the idea that diets rich in this compound may prove beneficial.     

Solution Thermodynamics of Piroxicam in some Ethanol + Water Mixtures and Correlation with the Jouyban–Acree Model

The solubility of piroxicam (PIR) in several ethanol + water mixtures was determined at five temperatures from 293.15 to 313.15 K. The thermodynamic functions; Gibbs energy, enthalpy, and entropy of solution and of mixing were obtained from these solubility data and the drug properties of fusion by using the van’t Hoff and Gibbs equations. The greatest solubility value was obtained in pure ethanol. A non-linear enthalpy–entropy relationship was observed from a plot of enthalpy versus Gibbs energy of solution. Accordingly, the driving mechanism for PIR solubility in water-rich mixtures is the entropy, probably due to water-structure loss around the drug’s non-polar moieties by ethanol, whereas, in ethanol-rich mixtures the driving mechanism is the enthalpy, probably due to better PIR solvation by the co-solvent molecules. The solubilities and the derived thermodynamic properties in mixed solvents were correlated using the Jouyban–Acree model.     

Sulfinylnitriles: Sulfinyl–Metal Exchange–Alkylation Strategies

Adding organolithiums, Grignard reagents, or zincates to sulfinylnitriles triggers a facile sulfinyl–metal exchange to afford N‐ or C‐metalated nitriles. Sulfinyl–magnesium exchange–alkylations efficiently install quaternary and tertiary centers, even in the case of tertiary sulfinylnitriles that contain a highly acidic methine proton. α‐Sulfinylalkenenitriles afford moderately nucleophilic magnesiated nitriles, and the reactivity can be dramatically increased by conversion to the corresponding magnesiates. The sulfinyl‐metal exchange is extremely fast, proceeds efficiently with quaternary, tertiary, and vinylic α‐sulfinylnitriles, and exhibits an exceptional functional group tolerance in nitrile alkylations.     

Thermodynamics of partitioning of benzocaine in some organic solvent/buffer and liposome systems

The thermodynamics of partitioning of benzocaine (BZC) were studied in octanol/buffer (ROH/W), isopropyl myristate/buffer (IPM/W), cyclohexane/buffer (CH/W), and dimyristoyl phosphatidylcholine (DMPC) and dipalmitoyl phosphatidylcholine (DPPC) liposome systems. In all cases the partition coefficients were greater than unity; therefore the free energies of transfer were negative, that is, the processes of transfer of BZC from aqueous media to organic systems were spontaneous. The partition coefficients were approximately three-fold higher in DMPC liposomes compared with the ROH/W system in the 30 degrees -40 degrees C temperature range. The enthalpies of transfer from aqueous media to ROH and IPM were negative, but positive for CH, while this property was negative for DMPC liposomes and positive for DPPC liposomes. The entropies of transfer were positive in almost all cases, except for DMPC. The results presented here confirm the lipophilic nature of BZC.