Synthesis,crystal structure,spectroscopy, thermal properties and carbonic anhydrase activities of new metal(II) complexes with mefenamic acid and picoline derivatives

The mononuclear six metal(II) complexes ([Co(mef)₂(3-pic)₂(CH₃OH)₂] (1), [Ni(mef)₂(3-pic)₂(CH₃OH)₂] (2), [Cu(mef)₂(3-pic)₂] (3), [Co(mef)₂(4-pic)₂] (4), [Ni(mef)₂(4-pic)₂] (5), and [Cu(mef)₂(4-pic)₂] (6) with mefenamic acid and picoline ligands were synthesized, characterized, and their carbonic anhydrase inhibitory activities were evaluated. The six complexes were characterized by elemental analysis, FT-IR spectroscopy, and thermal analyses. The crystal structures of 1, 3, and 6 were determined by X-ray crystallography. The complexes have octahedral geometry. In 1, the mefenamato ligand behaved as monodentate whereas in 3 and 6, the mefenamato ligand acted as a bidentate ligand. Complexes 3 and 6 consist of the mefenamate and 4-picoline ligands. In 1, unlike the other complexes, methanol acted as a ligand and was involved in the coordination. Carbonic anhydrase I and II isoenzymes were purified from human erythrocytes. The in vitro effects of mefenamic acid, 3-picoline, 4-picoline, and the six metal(II) complexes on these isoenzymes were evaluated.     

Impacts of uniaxial elongation on the bandstructures of two-dimensional sonic crystals and associated applications

Influences of uniaxial elongation along the [11] direction of triangular and [10] direction of square sonic crystals under the constraint of conserved unit cell area are investigated by examining band structures and equi-frequency contours. Lowest-lying band gap of the triangular lattice observed at high filling fractions diminishes for negative elongation (compression), whereas another band gap develops at lower frequencies whose width reaches appreciable values for moderate elongation. The band gap of the square lattice, which appears at high filling fractions, is modified slightly with elongation. Frequency ranges of the bands, and thus the group velocities along the high-symmetry directions, vary with elongation which may be useful in applications like slow sound propagation. Elongation is observed to modify the equi-frequency contours significantly through reducing the lattice symmetry. The most prominent impact is the transformation of closed contours into open ones, whereas the rest are stretched either along or normal to the elongation axis of the 1st Brillouin Zone. This observation is utilized to implement wide-band all-angle self-collimation and superprism effect, which are demonstrated through Finite-Element computations.     

Nanoparticle‐Driven Orientation Transition and Soft‐Shear Alignment in Diblock Copolymer Films via Dynamic Thermal Gradient Field

Sharp dynamic thermal gradient (∇T ≈ 45 °C mm⁻¹) field‐driven assembly of cylinder‐forming block copolymer (c‐BCP) films filled with PS‐coated gold nanoparticles (AuNPs; d_NP ≈ 3.6 nm, φ_NP ≈ 0–0.1) is studied. The influence of increasing AuNP loading fraction on dispersion and assembly of AuNPs within c‐BCP (PS‐PMMA) films is investigated via both static and dynamic thermal gradient fields. With φ_NP increasing, a sharp transition from vertical to random in‐plane horizontal cylinder orientation is observed due to enrichment of AuNPs at the substrate side and favorable interaction of PMMA chains with gold cores. Furthermore, a detachable capping elastomer layer can self‐align these random oriented PMMA microdomains into unidirectional hybrid AuNP/c‐BCP nanolines, quantified with an alignment order parameter, S.

     

Synthesis,characterization, catalase functions and DNA cleavage studies of new homo and heteronuclear Schiff base copper(II) complexes

A new tetradentate diimine–dioxime ligand containing a donor set of N₄, and its homo-, heterodinuclear and homotrinuclear copper(II) complexes were prepared and characterized on the basis of their elemental analysis, FT-IR, ¹H and ¹³C NMR spectra, molar conductivity and magnetic moment measurements. The extraction ability of N,N′′-bis[1-biphenyl-2-hydroxyimino-1-ethylidene]-diethylenetriamine was also evaluated in chloroform by using several transition metal picrates such as Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II), Cd(II) and Hg(II). It has been seen that the ligand shows strong binding ability toward the copper(II) ion. Moreover, the catalytic activities of the complexes for the disproportionation of hydrogen peroxide were investigated in the presence of imidazole. The synthesized complexes display efficiency in the disproportion reactions of hydrogen peroxide, producing water and dioxygen in catalase-like activity. The interaction between these complexes and DNA has also been investigated by agarose gel electrophoresis. We found that the homo- and heterodinuclear copper complexes can cleave supercoiled pBR322 DNA to nicked and linear forms. The dinuclear complexes including phenanthroline (2–4), with H₂O₂ as a co-oxidant, exhibited the strongest cleaving activity.     

Inverse scattering on the half-line for generalized ZS-AKNS system with general boundary conditions

The inverse scattering problem for a first order system of three equations on the half-line with nonsingular diagonal matrix multiplying the derivative and general boundary conditions is considered. It is focused the case of two repeated diagonal elements of diagonal matrix. The scattering matrix on the half line is defined and a unique restoration of the potential from the scattering matrix is proved. The possible application to integration of integro-differential four-wave interaction problem is also focused.     

Polarization-independent beam splitting by a photonic crystal right prism

Splitting of light waves by a two-dimensional photonic crystal associated with source size and dispersion relation of photonic crystal at a wavelength of 1,550 nm without disturbing periodicity is numerically demonstrated via finite-difference time-domain simulations. Split branches in either polarization state make plus or minus 45° with the [11] direction and propagate in a self-collimated manner with equal amplitude and phase. Sixty-four percent of total transmittance is attained provided that the waves are coupled and collected through appropriate planar waveguides. Alternatively, approximately 50 % total transmittance for both polarizations can be obtained by application of an anti-reflection coating layer at the input face. Polarization-independent beam splitting occurs in a narrow range around the target wavelength, while its transverse-magnetically polarized sub-harmonic can also be split. The photonic crystal can also operate as a polarizing splitter at oblique incidence.     

Modification of sialic acid-MBTH assay for quantitative determination of nonenzymatically glucosylated proteins

A colorimetric assay for the quantitative determination of nonenzymatically glucosylated proteins is presented. The method employed is a modification of the method of Massamiri et al. (1978, Anal. Biochem., 91, 618–625) for quantitating sialic acid residues. The procedure involves periodate oxidation of the glucosylated protein releasing formaldehyde. The latter is then detected by complexing with the reagent, 3-methyl-2-benzothiazolinone hydrazone (MBTH). Fructose is used as a standard as it is structurally analogous to the ketoamine form on the protein. The MBTH assay can accurately detect fructose in concentrations as low as 1 μM. The assay was utilized to quantitate in vitro nonenzymatically glucosylated calmodulin and bovine serum albumin.     

Effects of European mistletoe (Viscum album L. subsp. album) extracts on activity rhythms of the Syrian hamsters (Mesocricetus auratus)

Antitumor drugs may have some significant nervous system side-effects such as disrupted sleep, eating and drinking patterns. European Mistletoe has been investigated for many decades for its potential use against cancer. To test the hypothesis that the non-antineoplastic effects of mistletoe might be mediated by the actions on the circadian timing system, we have applied mistletoe extracts and vehicle and have measured locomotor activity, feeding and drinking rhythms under constant darkness. Four groups (vehicle, 20 mg kg(-1) ip injection, 40 mg kg(-1) ip injection and 6 g kg(-1) oral administration) were performed for both heat-treated and freeze-dried extracts. None of the administrations changed the locomotor activity, feeding and drinking rhythms in the groups except for 40 mg kg(-1) freeze-dried injected group. The locomotor activity levels decreased in 40 mg kg(-1) freeze-dried extract injected group. These results suggest that, side-effects of mistletoe on circadian timing system of the Syrian hamster depend on the dose and the preparation method of the extract.     

Identification of redox sensitive thiols of protein disulfide isomerase using isotope coded affinity technology and mass spectrometry

Regulation of the redox state of protein disulfide isomerase (PDI) is critical for its various catalytic functions. Here we describe a procedure utilizing isotope-coded affinity tag (ICAT) technology and mass spectrometry that quantitates relative changes in the dynamic thiol and disulfide states of human PDI. Human PDI contains six cysteine residues, four present in two active sites within the a and a' domains, and two present in the b' domain. ICAT labeling of human PDI indicates a difference between the redox state of the two active sites. Furthermore, under auto-oxidation conditions an approximately 80% decrease in available thiols within the a domain was detected. Surprisingly, the redox state of one of the two cysteines, Cys-295, within the b' domain was altered between the fully reduced and the auto-oxidized state of PDI while the other b' domain cysteine remained fully reduced. An interesting mono- and dioxidation modification of an invariable tryptophan residue, Trp-35, within the active site was also mapped by tandem mass spectrometry. Our findings indicate that ICAT methodology in conjunction with mass spectrometry represents a powerful tool to monitor changes in the redox state of individual cysteine residues within PDI under various conditions.     

An amperometric biosensor based on multiwalled carbon nanotube-poly(pyrrole)-horseradish peroxidase nanobiocomposite film for determination of phenol derivatives

An amperometric biosensor based on horseradish peroxidase (HRP) and carbon nanotube (CNT)/polypyrrole (PPy) nanobiocomposite film on a gold surface has been developed. The HRP was incorporated into the CNT/PPy nanocomposite matrix in one-step electropolymerization process without the aid of cross-linking agent. Amperometric response was measured as a function of concentration of phenol derivatives, at a fixed bias voltage of -50 mV. Optimization of the experimental parameters was performed with regard to pH and concentration of hydrogen peroxide. The linear range, sensitivity and detection limit of the biosensor were investigated for eighteen phenol derivatives. The sensitivity in the linear range increased in this order: 4-methoxyphenol>2-aminophenol>guaiacol=m-cresol>2-chlorophenol=4-chlorophenol=hydroquinone=pyrocatechol>2,6-dimethoxyphenol>3-chlorophenol>p-cresol>p-benzoquinone=4-acetamidophenol>catechol>phenol=pyrogallol=2,4-dimethylphenol. CNTs was shown to enhance the electron transfer as a mediator and capable to carry higher bioactivity owing to its intensified surface area. The biosensor exhibited low detection limits with a short response time (2s) for the tested phenolics compared to the reported working electrodes. It retained 70% of its initial activity after using for 700 measurements in 1 month.