Modulating protein structure with fluorous amino acids: increased stability and native-like structure conferred on a 4-helix bundle protein by hexafluoroleucine

There has recently been much interest in exploiting the unusual properties associated with fluorocarbons to modulate the physicochemical properties of proteins. Here we present a detailed investigation into the effect on structure and stability of systematically repacking the hydrophobic core of a model protein with the extensively fluorinated (fluorous) amino acid l-5,5,5,5',5',5'-hexafluoroleucine (hFLeu). The starting point was a 27-residue peptide, alpha(4)-H, that adopts an antiparallel 4-alpha-helix bundle structure, and in which the hydrophobic core comprises six layers of leucine residues introduced at the "a" and "d" positions of the canonical heptad repeat. A series of peptides were synthesized in which the central two (alpha(4)-F(2))(,) four (alpha(4)-F(4)), or all six layers (alpha(4)-F(6)) of the core were substituted hFLeu. The free energy of unfolding increases by 0.3 (kcal/mol)/hFLeu on repacking the central two layers and by an additional 0.12 (kcal/mol)/hFLeu on repacking additional layers, so that alpha(4)-F(6) is approximately 25% more stable than the nonfluorinated protein alpha(4)-H. One-dimensional proton, two-dimensional (1)H-(15)N HSQC, and (19)F NMR spectroscopies were used to examine the effect of fluorination on the conformational dynamics of the peptide. Unexpectedly, increasing the degree of fluorination also appears to result in peptides that possess a more structured backbone and less fluid hydrophobic core. The latter only occurs in alpha(4)-F(4) and alpha(4)-F(6), suggesting that crowding of the hFLeu residues may restrict the amplitude and/or time scales for rotation of the side chains.     

Flow Reversal of Fully-Developed Mixed MHD Convection in Vertical Channels

The present analysis is concerned with flow reversal phenomena of the fully-developed laminar combined free and forced MHD convection in a vertical parallel-plate channel. The effect of viscous dissipation is taken into account. Flow reversal adjacent to the cold （or hot） wall is found to exist within the channel as Gr/Re is above （or below） a threshold value. Parameter zones for the occurrence of reversed flow are presented.     

Sintering temperature dependence of room temperature magnetic and dielectric properties of Co0.5Zn0.5Fe2O4 prepared using mechanically alloyed nanoparticles

Co_0.5Zn_0.5Fe₂O₄ nanoparticles were prepared using mechanical alloying (MA) and sintering. The crystallite size, coercivity, retentivity and saturation magnetization were also measured. The frequency dependence of dielectric and the magnetic parameters, namely, real permittivity ε′, loss tanget tan δ, real permeability μ′ and loss factor μ″ were measured at room temperature for samples sintered from 600 to 1000 °C, in the frequency range 10 MHz to 1.0 GHz. The results show that the crystallite size of the resulting products ranges between 16 and 67 nm for as-milled sample and the sample sintered at 1000 °C, respectively. The sample sintered at 1000 °C, measured at room temperature exhibited a saturation magnetization of 37 emu g⁻¹. The values of permittivity remain constant within the measured frequency, but vary with sintering temperature. The permeability values, on the other hand however vary with both the sintering temperature and the frequency, thus, the absolute value of the permeability decreased after the natural resonance frequency.     

Fluorescence Quantum Yield Determination of Propylparaben Using Flow Injection Spectroscopy

The determination of the fluorescence quantum yield of Propylparaben is introduced and applied to L-tyrosine as a standard by a new approach that can be applied to the pharmaceutical compound utilised in this study. The quantum yield is a critical figure of quality for the optical nature of a fluorophore. Numerous investigations have considered the glitter in both pharmaceutical and nature compounds for its medical and industrial significance. A straightforward method is detailed here to decide the quantum yield of Propylparaben in solution as an element of the fluorescence concentration. For this reason, L-Tyrosine is chosen as a fluorescence standard perspective to gauge the Propylparaben fluorescence quantum yield. The impacts of pH, solvents and flow rate on the assessment of quantum yield and quantum efficiency, for the reference and the solutions of Propylparaben, have been investigated. The results indicated that these parameters significantly influence the accuracy of the method. Diverse methods are concentrated on to represent distinctive quantum yield advancements with the quantum efficiency. The impact of these parameters was likewise considered. In this study, the application of the single method may be taken into consideration to compute quantum yield of Propylparaben, which was 0.36, and this is an exceptionally basic and general technique to solve the imperative issue of luminescence quantum yield assurance of other fluorescence compounds.     

5‐Phenyl‐1,3,4‐oxadiazole‐2‐thiol/polyamide‐montmorillonite microbicides nanocomposites as drug delivery system

The preparation and structural characterization of polymeric microbicides consisting of 5‐phenyl‐1,3,4‐oxadiazole‐2‐thiol covalently bound to polyamide based on diethyl‐2,3‐dihydroxysuccinate and polyoxypropylenetriamine Jeffamine (T₄₀₃) are described. Two different mole ratios of 5‐phenyl‐1,3,4‐oxadiazole‐2‐thiol was reacted with chloroacetylated diethyl‐2,3‐dihydroxysuccinate followed by polycondensation with Jeffamine (T₄₀₃). The nanocomposites were prepared by modification of microbicide polyamides to yield polymers with phosphonium salt or amine hydrochloride salt followed by ion exchange process between the phosphonium salt or amine hydrochloride of the polyamides and the intermellar sodium cation of the clay mineral montmorillonite. The monomers were characterized by mass spectrum, proton nuclear magnetic resonance. The polymers showed good or moderate antimicrobial activities. Nanocomposites were characterized by Fourier transformed infrared spectroscopy, X‐ray diffraction, thermal gravimetric analysis, and transmission electron microscope. The swelling behavior and release of 5‐phenyl‐1,3,4‐oxadiazole‐2‐thiol in different pH values (2.3, 5.8, and 7.4) were studied. A slow release, ranging from 12% to 28% after 50 hours was recorded from nanocomposites. However, the release profile reached almost 70% from polyamides. The antimicrobial activity of the polyamides was studied against gram‐negative bacteria, gram‐positive bacteria, yeast, and the filamentous fungi by well diffusion method. The polyamides showed better antimicrobial activities than 5‐phenyl‐1,3,4‐oxadiazole‐2‐thiol.     

A note on the polynomial decay of a weakly dissipative viscoelastic system

In this note we study an abstract class of weakly dissipative second-order systems with finite memory. We establish the polynomial decay of Rivera, Naso and Vegni for the solution of the system under a very weak condition on the relaxation function.     

Statistical relationship between activity concentrations of radionuclides 226Ra, 232Th, 40K,and 137Cs and geological formations in surface soil of Jordan

An extensive study was conducted to determine the activity concentrations of natural and artificial radionuclides ²²⁶Ra, ²³²Th, ⁴⁰K, and ¹³⁷Cs in soil samples of each governate of Jordan. A total of 370 samples have been measured using a high-purity germanium detector. The activity concentration for ²²⁶Ra, ²³²Th, ⁴⁰K, and ¹³⁷Cs has mean values of 42?±?3, 23?±?3, 309?±?21, and 3.7?±?0.9 Bq kg^–1, respectively. The highest mean activity concentration for ²²⁶Ra was found to be 138?±?4 Bq kg^–1 in the Alkarak governate. In the Ajloun and Jarash governates, the highest mean activity concentration was 35?±?3 Bq kg^–1 for ²³²Th, and 14.2?±?1.9 Bq kg^–1 for ¹³⁷Cs, respectively. Geological influence on the activity concentrations was investigated using the one-way analysis of variance (ANOVA) and independent samples. The ANOVA results indicate that there are strong significant differences between the activity concentrations of ²³²Th, ⁴⁰K, and ¹³⁷Cs based on geological formations the radionuclides occur. The main contribution to gamma dose rate was due to ²²⁶Ra activity concentration. Radium equivalent and external hazard index are associated with a mean value of 98 Bq kg^–1, and 0.266, respectively.     

Aberrant expression of acute-phase reactant proteins in sera and breast lesions of patients with malignant and benign breast tumors

We have analyzed unfractionated sera of newly diagnosed patients (n=10) with breast carcinoma (BC), prior to treatment, and patients (n=5) with fibrocystic disease of the breast (FDB) by two-dimensional gel electrophoresis (2-DE) and silver staining. The patients' 2-DE serum protein profiles obtained were then subjected to image analysis and compared to similar data generated from sera of normal healthy female controls (n=10) of the same range of age. The relative expression of alpha1-antichymotrypsin (ACT), clusterin, and complement factor B was significantly higher in all BC patients as compared to normal controls. However, the expression of alpha1-antitrypsin (AAT) in BC patients was apparently lower than that of the controls. Similar differential expression of ACT was detected in the FDB patients. The aberrant expression of the serum acute-phase proteins of patients with BC and FDB was confirmed by competitive enzyme-linked immunosorbent assay (ELISA). Similar altered proteins expression was also observed from immunohistochemical studies of malignant (n=5) and benign (n=5) breast lesions of the respective patients performed using antisera to the aberrantly expressed proteins. However, the malignant breast lesions were instead positively stained for AAT. The differential expression of the serum proteins was apparently abrogated when a six-month follow-up study was performed on nine of the BC patients subsequent to treatment.     

Dielectric permittivity of nickel ferrites at microwave frequencies 1 MHz to 1.8 GHz

NiFe₂O₄ prepared via the sol–gel technique were pre-sintered at 900 °C and synthesized at different sintering temperatures from 1,000 °C to 1,200 °C at 100 °C intervals. The samples were characterized for microwave dielectric properties. These samples were measured using Agilent Impedance/Material Analyzer at frequencies 1 MHz to 1.8 GHz. Results showed a decrease in the dielectric constant and loss factor with frequency except at the turning point, around 150 MHz, where the loss factor showed a gradual increase. However, both the dielectric constant and loss factor increase with increasing sintering temperature. The grain size and density also increased with increasing sintering temperature, but the porosity and grain boundary density showed a decrease. This paper was presented at the International Conference on Solid State Science and Technology 2006, Kuala Terengganu, Malaysia, Sept. 4–6, 2006.