Synthesis,Characterization and Redox Properties of Three New <Emphasis Type="Italic">vic</Emphasis>-dioximes and their Nickel(II) Metal Complexes

Three novel vic-dioximes: cyclohexylamine-p-tolylglyoxime (L₁H₂), t-butylamine-p-tolylglyoxime (L₂H₂) and sec-butylamine-p-tolylglyoxime (L₃H₂) were prepared by the reaction of anti-p-tolylchloroglyoxime with cyclohexylamine, t-butylamine and sec-butylamine in absolute THF. The detection of H-bonding in all of the Ni(II) complexes by i.r. revealed the square-planar MN₄ coordination of mononuclear complexes. MN₄ coordination of the [(L₁H)₂Ni] complex was also determined by ¹H and ¹³C-n.m.r spectroscopy. Mononuclear complexes with a 1:2 metal-ligand ratio were prepared using Ni(II) salts. All Ni(II) complexes are insoluble in common solvents. The ligands and complexes were characterized by elemental analyses, FT-i.r., u.v.–vis., ¹H and ¹³C-n.m.r. spectra, magnetic susceptibility measurements, thermogravimetric analyses (t.g.a.) and cyclic voltammetry.     

Synthesis, Spectral Characterization and Electrochemical Properties of New vic-dioxime Complexes Bearing Carboxylate

Three new vic-dioxime ligands, [N-(ethyl-4-amino-1-piperidine carboxylate)-phenylglyoxime (L¹H₂), N-(ethyl-4-amino-1-piperidine carboxylate)-glyoxime (L²H₂), and N,N′-bis(ethyl-4-amino-1-piperidine carboxylate)-glyoxime (L³H₂)], and their Co(II) with Cu(II) metal complexes, were synthesized for the first time. Mononuclear complexes of these ligands with a 1:2 metal-ligand ratio were prepared with Co(II) and Cu(II) salts. The BF₂⁺-capped Co(II) and mononuclear complexes of the vic-dioxime were prepared for [Co(L¹·BF₂)₂] and [Co(L²·BF₂)₂]. The ligands act in a polydentate fashion bonding through nitrogen atoms in the presence of a base, as do most vic-dioximes. The cobalt(II) and copper(II) complexes are non-electrolytes as shown by their molar conductivities (Λ_M) in DMF. The structures of the ligands and complexes were determined by elemental analyses, FT-i.r., u.v.–vis., ¹H- and ¹³C-n.m.r. spectra, magnetic susceptibility measurements, and molar conductivity. The comparative electrochemical studies show that the stabilities of the reduced or oxidized species and the electrode potentials of the complexes are affected by the substituents attached on the oxime moieties of the complexes.     

A Novel Flow-injection Rhodium Nanoparticles Modified Phosphate Biosensor and its Operation in Artificial Urine

A biosensor for phosphate determination with the flow-injection system was developed using rhodium nanoparticles modified Poly(pyrrole-co-[1-(2-aminophenyl) pyrrole])/pyruvate oxidase. The biosensor showed a very wide linearity up to 70 mM phosphate concentration compared to previously reports, response time of 4 s., operational stability with a relative standard deviation of 0.009 % and accuracy of 99.4 %±0.949 at a flow rate of 2.0 Ml min.⁻¹ at exactly −0.68 V. Detection limit were calculated to be 21±0.001 μM by preserving 81.1 % of its initial response at the end of 16^th days. Artificial urine was analyzed without dilution to investigate biosensor performance.     

The sterically hindered salicylaldimine ligands with their copper(II) metal complexes: Synthesis,spectroscopy, electrochemical and thin-layer spectroelectrochemical features

The synthesis, structure, spectroscopic and electro-spectrochemical properties of sterically constrained Schiff-base ligands (L_nH) (n = 1, 2, and 3) (L = N-[m-(methylmercapto)aniline]-3,5-di-t-butylsalicylaldimine, m = 4, 3, and 2 positions, respectively) and their copper(II) complexes [Cu(L_n)₂] are described. Three new dissymmetric bidentate salicylaldimine ligands containing a donor set of ONNO were prepared by reaction of different primary amine with 3,5-di-t-butyl-2-hydroxybenzaldehyde (3,5-DTB). The copper(II) metal complexes of these ligands were synthesized by treating an methanolic solution of the appropriate ligand with an equimolar amount of Cu(Ac)₂ · H₂O. The ligands and their copper complexes were characterized by FT-IR, UV–Vis, ¹H and ¹³C NMR and elemental analysis methods in addition to magnetic susceptibility, molar conductivity, and spectroelectrochemical techniques. Analytical data reveal that copper(II) metal complexes possess 1:2 metal–ligand ratios. On the basis of molar conductance, the copper(II) metal complexes could be formulated as [Cu(L_n)₂] due to their non-electrolytic nature in dimethylforamide (DMF). The room temperature magnetic moments of [Cu(L_n)₂] complexes are in the range of 1.82–1.90 B.M which are typical for mononuclear of Cu(II) compounds with a S = 1/2 spin state. The complexes did not indicate antiferromagnetic coupling of spin at this temperature. Electrochemical and thin-layer spectroelectrochemical studies of the ligands and complexes were comparatively studied in the same experimental conditions. The results revealed that all ligands displayed irreversible reduction processes and the cathodic peak potential values of (L₃H) are shifted towards negative potential values compared to those of (L₁H) and (L₂H). It is attributed to the weak-electron-donating methyl sulfanyl group substituted on the ortho (m = 2) position of benzene ring. Additionally, all copper complexes showed one quasi-reversible one-electron reduction process in the scan rates of 0.025–0.50 V s⁻¹, which are assigned to simple metal-based one-electron processes; [Cu(2+)(L_n)₂] + e⁻ → [Cu(1+)(L_n)₂]⁻. The spectral changes corresponding to the ligands and complexes during the applied potential in a thin-layer cell confirmed the ligand and metal-based reduction processes, respectively.     

An adaptive dynamic relaxation method for quasi-static simulations using the peridynamic theory

The peridynamic theory is advantageous for problems involving damage since the peridynamic equation of motion is valid everywhere, regardless of existing discontinuities, and an external criterion is not necessary for predicting damage initiation and propagation. However, the current solution methods for the equations of peridynamics utilize explicit time integration, which poses difficulties in simulations of most experiments under quasi-static conditions. Thus, there is a need to obtain steady-state solutions in order to validate peridynamic predictions against experimental measurements. This study presents an extension of dynamic relaxation methods for obtaining steady-state solutions of nonlinear peridynamic equations.     

Carbon nanofiber based CuO nanorod counter electrode for enhanced solar cell performance and adsorptive photocatalytic activity

Journal of Nanoparticle Research - A comprehensive study of the antibacterial (bacteriostatic and bactericidal) properties of non-doped carbon nanodots (CNDs), nitrogen-doped (N-doped), and...     

Improved Sensing Performance of Amperometric Urea Biosensor by Using Platinum Nanoparticles

A novel Platinum nanoparticle (PtNPs) modified Poly(pyrrole-co-1-(2-Aminophenyl)pyrrole)/Urease film coated Au electrode was designed for amperometric detection of urea. PtNPs quantity, film density and pH were optimized and interference effect of some substances readily found in municipal wastewater and blood was investigated. The biosensor responded to urea with a measurement concentration range of 0.1 to 30 mM, a sensitivity of 31.8 μA mM⁻¹ cm⁻², a LOD of 7.58 μM, an accuracy of 104 % and a RSD% of only 0.82. It sensed the concentration of urea in the municipal sewage water with recovery of 97.6 % (n=3) and remained 78 % of its initial response at 28^th day. Results confirmed that PtNPs with strong conductivity improved the electron transfer ability of the working electrode.     

Experimental and Theoretical Vibrational Spectra of Sideridiol Isolated from <Emphasis Type="Italic">Sideritis</Emphasis> Species

Sideridiol (ent-7α,18β-dihydroxykaur-15-ene) one of the ent-kaurene diterpenoid, is isolated from the genus Sideritis L. belongs to the family of Lamiaceae. The vibrational frequencies of sideridiol in the ground state have been calculated using the Density Functional Theory (DFT) method with the 6-31G(d) and 6 31+G(d,p) basis sets. The calculated vibrational frequencies have been compared with that of obtained experimental IR spectrum.     

Distributed computing strategies for processing of FT-ICR MS imaging datasets for continuous mode data visualization

High-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry imaging enables the spatial mapping and identification of biomolecules from complex surfaces. The need for long time-domain transients, and thus large raw file sizes, results in a large amount of raw data (“big data”) that must be processed efficiently and rapidly. This can be compounded by large-area imaging and/or high spatial resolution imaging. For FT-ICR, data processing and data reduction must not compromise the high mass resolution afforded by the mass spectrometer. The continuous mode “Mosaic Datacube” approach allows high mass resolution visualization (0.001 Da) of mass spectrometry imaging data, but requires additional processing as compared to feature-based processing. We describe the use of distributed computing for processing of FT-ICR MS imaging datasets with generation of continuous mode Mosaic Datacubes for high mass resolution visualization. An eight-fold improvement in processing time is demonstrated using a Dutch nationally available cloud service.

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