Synthesis,characterization, and evaluation of biological activities of new 4′‐substituted ruthenium (II) terpyridine complexes: Prospective anti‐inflammatory properties

The synthesis and characterization of Ru (II) terpyridine complexes derived from 4′ functionalized 2,2′:6′,2″‐terpyridine (tpy) ligands are reported. The heteroleptic complexes comprise the synthesized ligands 4′‐(2‐thienyl)‐ 2,2′:6′,2″‐terpyridine) or (4′‐(3,4‐dimethoxyphenyl)‐2,2′:6′,2″‐terpyridine and (dimethyl 5‐(pyrimidin‐5‐yl)isophthalate). The new complexes [Ru(4′‐(2‐thienyl)‐2,2′:6′,2″‐terpyridine)(5‐(pyrimidin‐5‐yl)‐isophthalic acid)Cl₂] ( 9 ), [Ru(4′‐(3,4‐dimethoxyphenyl)‐2,2′:6′,2″‐terpyridine)(5‐(pyrimidin‐5‐yl)‐isophthalic acid)Cl₂] ( 10 ), and [Ru(4′‐(2‐thienyl)‐2,2′:6′,2″‐terpyridine)(5‐(pyrimidin‐5‐yl)‐isophthalic acid)(NCS)₂] ( 11 ) were characterized by ¹H‐ and ¹³C‐NMR spectroscopy, C, H, N, and S elemental analysis, UPLC‐ESI‐MS, TGA, FT‐IR, and UV‐Vis spectroscopy. The biological activities of the synthesized ligands and their Ru (II) complexes as anti‐inflammatory, antimicrobial, and anticancer agents were evaluated. Furthermore, the toxicity of the synthesized compounds was studied and compared with the standard drugs, namely, diclofenac potassium and ibuprofen, using hemolysis assay. The results indicated that the ligands and the complex 9 possess superior anti‐inflammatory activities inhibiting albumin denaturation (89.88–100%) compared with the standard drugs (51.5–88.37%) at a concentration of 500 μg g^?1. These activities were related to the presence of the chelating N‐atoms in the ligands and the exchangeable chloro‐ groups in the complex. Moreover, the chloro‐ and thiophene groups in complex 9 produce a higher anticancer activity compared with its isothiocyanate derivative in the complex 11 and the 3,4‐dimethoxyphenyl moiety in complex 10 . Considering the toxicity results, the synthesized ligands are nontoxic or far less toxic compared with the standard drugs and the metal complexes. Therefore, these newly synthesized compounds are promising anti‐inflammatory agents in addition to their moderate unique broad antimicrobial activity.     

Development of a Novel Automatic Potentiometric System for Determination of Selenium and Its Application in Pharmaceutical Formulations and Anodic Slime

Poly(vinyl chloride) polymeric membrane sensors containing Sn(IV) phthalocyanine dichloride (SnPC) and Co(II) phthalocyanine (CoPC) as novel electroactive materials dispersed in o‐nitrophenyl octylether (o‐NPOE) as a plasticizer are examined potentiometrically with respect to their response toward selenite (SeO₃^2?) ions. Fast Nernstian response for SeO₃^2? ions over the concentration ranges 7.0×10^?6–1.0×10^?3 and 8.0×10^?6–1.0×10^?3 mol L^?l at pH 3.5–8.5 with lower detection limit of 5.0×10^?6 and 8.0×10^?6 mol L^?1 and calibration slopes of ?25.4 and ?29.7 mV decade^?1 are obtained with SnPC and CoPC based membrane sensors, respectively. The proposed sensors reveals by the modified separate solution method (MSSM) a good selectivity over different anions which differ significantly from the classical Hofmeister series. A segmented sandwich membrane method is used to determine complex formation constants of the ionophores in situe in the solvent polymeric sensing membranes. Membrane incorporating CoPC in a tubular flow detector is used in a two channels flow injection set up for continuous monitoring of selenite at a frequency of ca. 50 samples h^?1. Direct determination of selenium in pharmaceutical formulations and anodic slime gives results in good agreement with data obtained using standard ICP method.     

Lower Activation Energy for Catalytic Reactions through Host–Guest Cooperation within Metal–Organic Frameworks

Industrial synthesis is driven by a delicate balance of the value of the product against the cost of production. Catalysts are often employed to ensure product turnover is economically favorable by ensuring energy use is minimized. One method, which is gaining attention, involves cooperative catalytic systems. By inserting a flexible polymer into a metal–organic framework (MOF) host, the advantages of both components work synergistically to create a composite that efficiently fixes carbon dioxide to transform various epoxides into cyclic carbonates. The resulting material retains high yields under mild conditions with full reusability. By quantitatively studying the kinetic rates, the activation energy was calculated, for a physical mixture of the catalyst components to be about 50 % higher than that of the composite. Through the unification of two catalytically active components, a new opportunity opens up for the development of synergistic systems in multiple applications.     

Functionalization of α-Aminonicotinonitrile: A New Entry for Synthesis of Pyrazolo[3,4-b]pyridine,Pyrido[2,3-d]pyrimidine,and 1,8-Naphthyridine Derivatives

Russian Journal of General Chemistry - Functionalization of α-aminopyridine to a new series of pyridine and fused pyridine derivatives has been achieved via its reaction with a variety of...     

On the Dot Product Graph of a Commutative Ring

Let A be a commutative ring with nonzero identity, 1 ≤ n < ∞ be an integer, and R = A × A × … ×A (n times). The total dot product graph of R is the (undirected) graph TD(R) with vertices R* = R?{(0, 0,…, 0)}, and two distinct vertices x and y are adjacent if and only if x·y = 0 ∈ A (where x·y denote the normal dot product of x and y). Let Z(R) denote the set of all zero-divisors of R. Then the zero-divisor dot product graph of R is the induced subgraph ZD(R) of TD(R) with vertices Z(R)* = Z(R)?{(0, 0,…, 0)}. It follows that each edge (path) of the classical zero-divisor graph Γ(R) is an edge (path) of ZD(R). We observe that if n = 1, then TD(R) is a disconnected graph and ZD(R) is identical to the well-known zero-divisor graph of R in the sense of Beck–Anderson–Livingston, and hence it is connected. In this paper, we study both graphs TD(R) and ZD(R). For a commutative ring A and n ≥ 3, we show that TD(R) (ZD(R)) is connected with diameter two (at most three) and with girth three. Among other things, for n ≥ 2, we show that ZD(R) is identical to the zero-divisor graph of R if and only if either n = 2 and A is an integral domain or R is ring-isomorphic to ?₂ × ?₂ × ?₂.     

The direct determination of partial molar volumes and reaction volumes in ultra-dilute non-reactive and reactive multi-component systems using a combined spectroscopic and modified response surface model approach

Two experimental multi-component organometallic systems were studied, namely, (1) a non-reactive system consisting of [Mo(CO)(6)], [Mn(2)(CO)(10)], and [Re(2)(CO)(10)] in toluene under argon at 298.15 K and 0.1 MPa and (2) a reactive system consisting of [Rh(4)(CO)(12)] + PPh(3)--> [Rh(4)(CO)(11)PPh(3)] + CO in n-hexane under argon at 298.15 K and 0.1 MPa. The mole fractions of all solutes were less than 140 x 10(-6) in system (1) and less than 65 x 10(-6) in system (2). Simultaneous in-situ FTIR spectroscopic measurements and on-line oscillatory U-tube density measurements were performed on the multi-component solutions. A newly developed response surface methodology was applied to the data sets to determine the individual limiting partial molar volumes of all constituents present as well as the reaction volume. The limiting partial molar volumes obtained for system (1) were 176.4 +/- 2.5, 265.1 +/- 2.4, and 276.8 +/- 2.4 cm(3) mol(-1) for [Mo(CO)(6)], [Mn(2)(CO)(10)], and [Re(2)(CO)(10)], respectively and are consistent with independent binary experiments. The limiting partial molar volumes obtained for system (2) were 310.7 +/- 2.7, 219.8 +/- 2.2 and 461.5 +/- 4.5 cm(3) mol(-1) for [Rh(4)(CO)(12)], PPh(3) and [Rh(4)(CO)(11)PPh(3)], respectively. In addition, a reaction volume Delta(r)V equal to -17.0 +/- 5.7 cm(3) mol(-1) was obtained. The present results demonstrate that both partial molar volumes and reaction volumes can be obtained directly from multi-component organometallic solutions. This development provides a new tool for physico-chemical determinations relevant to a variety of solutes and their reactions.     

Development of stable extractive scintillating materials for real-time quantification of radiostrontium in aqueous solutions

Journal of Radioanalytical and Nuclear Chemistry - The research presented here is the development of sensor materials that are applicable for real-time in situ quantification of radiostrontium in...     

Protons colliding with crystalline ice: proton reflection and collision induced water desorption at low incidence energies

We present results of classical trajectory (CT) calculations on the sticking of protons to the basal plane (0001) face of crystalline ice, for normal incidence at a surface temperature (Ts) of 80 K. The calculations were performed for moderately low incidence energies (Ei) ranging from 0.05 to 4.0 eV. Surprisingly, significant reflection is predicted at low values of Ei (< or = 0.2 eV) due to repulsive electrostatic interactions between the incident proton and the surface water molecules with one of their H-atoms pointing upward toward the gas phase. The sticking probability increases with Ei and converges to unity for Ei > or = 0.8 eV. In the case of sticking, the proton is trapped in the ice forming a Zundel complex (H5O2+), with an average binding energy of 9.9 eV with a standard deviation of 0.5 eV, independent of the value of Ei. In nearly all sticking trajectories, the proton is implanted into the ice surface, with a penetration depth that increases with Ei. The strong interaction with the neighboring water molecules leads to a local rupture of the hydrogen bonding network, resulting in collision induced desorption of water (puffing), a process that occurs with significant probability even at the lowest Ei considered. The probability of water desorption increases with Ei. In nearly all trajectories in which water desorption occurs, a single three-coordinated water molecule is desorbed from the topmost monolayer.     

Synthesis and Evaluation of Some Schiff Base Surfactants for Treating Crude Oil Emulsions

Water soluble nonionic surfactants based on Schiff base monomers were prepared by their etherification with β,^` β- dichlorodiethylether and PEG 400 in presence of NaOH. The surface properties of the prepared surfactants were determined by measuring the surface tension at different temperatures. The prepared nonionic surfactants were evaluated as demulsifiers for synthetic water in crude-oil emulsions that were pronounced at different ratios of crude oil: water at 45°C and 60°C. The experimental results showed that the dehydration rate of the prepared demulsifiers reached 90% and 100% at some concentrations.     

Synthesis of Some Novel Nonionic Ethoxylated Surfactants Based on α-Amino Acids and Investigation of Their Surface Active Properties

Eight novel ethoxylated nonionic surfactants were prepared based on oil soluble α-amino acids. The L-phenylalanine and L-leucine were esterified and amidated with cetyl alcohol and palamitic acid, respectively; two amides and two esters of α-amino acids were obtained. The ethylene oxide was condensed with the prepared amides and esters to get three different polyethylene oxide units (40, 60, and 100) as phenylalanine derivatives. The amide and ester of α-L-leucine were ethoxylated at (60 ethylene oxides units). The analytical micro analysise, FTIR, ¹H NMR, ¹³C NMR, mass spectra were carried out to confirm the chemical structures. The surface tension of the water soluble prepared compounds was measured at 25°C, further the surface active properties were determined and calculated. Such that critical micelle concentration (CMC), surface excess (Γ_max); area per molecule (A_min), effectiveness (γ_CMC) free energy of micellization and adsorption (ΔG_mic, ΔG_ad). From the data obtained it was found that the CMC of phenylalanine esters is greater than that obtained for the amide derivatives. The Γ_max decreased as the ethylene oxide units (EO) increased. It was found also that the ΔG_ad was greater than the ΔG_mic. The obtained data and discrepancy were discussed on the light of surfactant chemical structure.