Reactivity of tris(acetylacetonato) iron(III) with tridentate [ONO] donor Schiff base as an access to newer mixed-ligand iron(III) complexes

Two new mixed-ligand iron(III) complexes, [Fe(L(n))(acac)(C(2)H(5)OH)] incorporating coordinated ethanol from the reaction solvent were accessed from the reaction of [Fe(acac)(3)] with [ONO] donor dibasic tridentate unsymmetrical Schiff base ligands derived from condensation of 2-hydroxy-1-napthaldehyde with 2-aminophenol (H(2)L(1)) or 2-aminobenzoic acid (H(2)L(2)). The thermal study (TGA-DTA) provided evidence for weakly bound ethanol which is readily substituted by neutral N-donor molecule imidazole, benzimidazole or pyridine to produce an array of newer complexes, [Fe(L(n))(acac)X] (n=1, 2; X=Im, Bim, Py). The compounds were characterized by elemental analyses, FT-IR, UV-vis, solution electrical conductivity, FAB mass, (1)H and (13)C NMR spectroscopy. Room temperature magnetic susceptibility measurements (μ(eff)～5.8 B.M.) are consistent with spin-free octahedral iron(III) complexes. Cyclic voltammetry of ethanol complexes revealed a quasi-reversible one electron redox response (ΔE(p)>100 mV) for the Fe(III)/Fe(II) couple. Low half wave redox potential (E(1/2)) values suggested easy redox susceptibility. The ground state geometries of the ethanol and imidazole complexes have been ascertained to be distorted octahedral by density functional theory using DMol3 program at BLYP/DNP level.     

Gas chromatography-electron ionization-mass spectrometry analysis of O,O'- dialkyl methylphosphonites for verification analysis of the Chemical Weapons Convention

Gas chromatography-mass spectrometry (GC-MS) analysis of O,O'-dialkyl methylphosphonites (DAMPs) was carried out with a view to developing a database and understanding the mechanism of fragmentation. DAMPs are included in the list of schedule 2B4 chemicals of the Chemical Weapons Convention. GC-MS analysis of DAMPs and their deuterated analogs revealed that their fragmentations were dominated by α-cleavages, alkenyl radical loss and hydrogen rearrangements. Based on fragment ions of deuterated analogs and density functional theory calculations, the fragmentation routes were rationalized.     

Composition of a monoterpenoid-rich essential oil from the rhizome of Zingiber officinale from north western Himalayas

The chemical composition of the essential oil from the rhizome of ginger (Zingiber officinale Roscoe), collected from Nahan, Himachal Pradesh, India, was determined by gas chromatography and GC-MS. Fifty-one compounds, representing 95.1% of the oil, were identified. The oil was characterized by relatively large amounts of the monoterpenoids 1,8-cineole (10.9%), linalool (4.8%), borneol (5.6%), alpha-terpineol (3.6%), neral (8.1%), geraniol (14.5%), geranial (9.5%), trans-dimethoxy citral (5.0%) and geranyl acetate (6.3%). Five compounds, namely trans-linalool oxide, trans-linalool oxide acetate, (Z)-dimethoxycitral, (E)-dimethoxy citral and epi-zingiberenol are reported for the first time in oil of ginger.     

Forward–Backward–Half Forward Dynamical Systems for Monotone Inclusion Problems with Application to v-GNE

Journal of Optimization Theory and Applications - In this paper, the first-order forward–backward–half forward dynamical systems associated with the inclusion problem consisting of...     

Phase diagram of two-dimensional binary Yukawa mixtures

We have used Ramakrishnan–Yussouff (RY) density functional theory (DFT) to explore the topology of the phase diagram of two-component charge stabilised colloidal suspensions confined to a two-dimensional plane. The particles of the system interact via purely repulsive soft core Yukawa potential. Pair correlation functions (PCFs) used as input informations in DFT were calculated by solving both the hypernetted chain (HNC) and Percus–Yevick (PY) integral equation theories. To test the relative performance of the HNC and PY theories in the context of phase transitions, we have also studied the corresponding one-component systems. We found that RY DFT with HNC PCFs does not stabilise solid in both the one- and two-component cases, whereas the PY theory does. By considering the freezing into the substitutionally disordered triangular solid, we found that the temperature-composition phase diagrams of the binary mixture are narrow spindles whose thickness depends on the symmetry of the mixture components and the value of the screening constant of the Yukawa potential. Although the phase diagram obtained by RY DFT with structural inputs calculated by the PY theory is found to be shifted to higher temperature region in the temperature-composition plane, however, it captures qualitatively all the essential features of the phase diagram. Our results are in principle verifiable through computer simulations and experiments.     

Chirped pulse amplification in single mode Tm:fiber using a chirped Bragg grating

We report femtosecond pulse generation and chirped pulse amplification in Tm:fiber. A mode-locked oscillator operating in the soliton regime produced 800 fs pulses with 5 nm spectral bandwidth, at 40 pJ pulse energy. This oscillator seeded a pre-amplifier that utilizes a Raman soliton self-frequency shift to produce wavelength tunable pulses with 3 nJ energy, reduced pulse duration of 150 fs, and increased bandwidth of 30 nm. For further amplification, the pulses were stretched up to 160 ps using a chirped Bragg grating (CBG). Stretched pulses were amplified to 85 nJ after compression in single-mode Tm:fiber and recompressed with the CBG as short as 400 fs. Compressed pulses were coupled into a highly nonlinear tellurite fiber to investigate the potential of this ultrashort pulse 2-μm fiber source as a pump for mid-IR supercontinuum generation.     

Improved Performance of an Amperometric Biosensor with Polydiaminonaphthalene on Electrochemically Deposited Au Nanoparticles

The performance of an enzyme sensor fabricated through covalent bond formation on the HRP‐bonded poly(1,8‐diaminonaphthalene) (polyDAN) layer with gold nanoparticles (AuNPs) was applied to catalyze the electrochemical reduction of H₂O₂. The surface characteristics of the sensor probe were studied using cyclic voltammetry, SEM, XPS, QCM, and impedance spectroscopy. The AuNP‐deposited surface resulted in higher conductivity and sensitivity for H₂O₂ detection in phosphate buffer solution. A linear calibration plot was obtained in the H₂O₂ concentration range between 10.0 μM and 25.0 mM with detection limit 5.0±1.25 μM. The lifetime of HRP/polyDAN/AuNP/GC probe was over 70 days without response loss.     

Ferrocenyl,Alkyl, and Aryl‐Pyrido[2,3‐d]Pyrimidines as Vasorelaxant of Smooth Muscle of Rat Aorta via cAMP Conservation Through Phosphodiesterase Inhibition

New pyrido[2,3‐d]pyrimidines 11 , 12 , 13 , and 21 have been synthesized. The vasorelaxant effect on smooth muscle isolated from rat aorta, via PDEs inhibition, of these compounds along with other pyrido[2,3‐d]pyrimidines 14 , 15 , 16 , 17 , 18 , 19 , 20 reported earlier by our group, has also been determined. These pyrido[2,3‐d]pyrimidines 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 were synthesized by the reaction of ferrocenyl‐ethynyl ketones ( 1 , 2 , 3 , 4 ) or α‐alkynyl ketones ( 5 , 6 , 7 , 8 , 9 , 10 ) with 6‐amino‐1,3‐dimethyluracil using [Ni(CN)₄]^?4 as an active catalytic species, formed in situ in a Ni(CN)₂/NaOH/H₂O/CO/KCN aqueous system. Evaluation of the vasorelaxant effect of compounds 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 demonstrated that all compounds relax the tissue in a concentration‐dependent manner. The structural changes do not alter the effectiveness; however, there are differences related to potency expressed as EC₅₀. Compounds 12 (7‐ferrocenyl‐1,3‐dimethyl‐5‐(m‐tolyl)‐pyrido[2,3‐d]pyrimidine) and 13 (7‐ferrocenyl‐1,3‐dipropyl‐5‐(4‐metoxyphenyl)‐pyrido[2,3‐d]pyrimidine) were the most potent compounds, even more than rolipram, reference drug; the EC₅₀ was 0.41 ± 0.02 μM and 0.81 ± 0.11 μM for 12 and 13 , correspondingly. The EC₅₀ of compounds 15 (7‐ferrocenyl‐1,3‐dimethyl‐5‐phenyl‐pyrido[2,3‐d]pyrimidine), 14 (7‐ferrocenyl‐5‐(3,5‐dimethoxyphenyl)‐1,3‐dimethylpyrido[2,3‐d]pyrimidine), and 19 (5‐n‐butyl‐7‐ethyl‐1,3‐dimethylpyrido[2,3‐d]pyrimidine) was similar to EC₅₀ of rolipram. Compounds 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 significantly induce concentration‐dependent vasorelaxation in endothelium‐intact aortic rings. In addition, the relaxation responses to each compound in either endothelium‐intact or endothelium denuded aortic rings were comparable, suggesting that removal of the functional endothelium has no significant influence on its intrinsic vasorelaxant activity. In vitro capability of conserving cyclic‐AMP or cyclic‐GMP (adenosine and guanosine 3′, 5′‐cyclic monophosphate) via PDE inhibition for compounds 12 , 13 , 14 , 15 and 19 was evaluated. Compounds 15 and 19 show the highest percent inhibition effect (94.83% and 83.98%, respectively) for the decomposition of c‐AMP. Docking studies showed that the compound 15 was selective for the inhibition of PDE‐4.     

Effect of annealing on the opto-electronic properties of Cu0.9In1.0Se2.0 films

The influence of annealing on the structure and opto-electronic properties of Cu_0.9In_1.0Se_2.0 films prepared by solution growth technique has been studied. The films annealed at 500–520°C in air, vacuum (10^?4 torr), In-vapour and Se-vapour show polycrystalline chalcopyrite structure with orientation perpendicular to the (220) plane. Films annealed in Se-vapour at 500°C for 30 min have maximum grain size (560 Å), minimum optical energy gap, maximum absorption coefficient, lowest resistivity, maximum photosensitivity and thus are suitable for photovoltaic applications. Annealing in In-vapour or in vacuum changesp-type CuInSe₂ inton-type which possibly arises due to the increase in Se vacancies.