A Four-Coordinate End-On Superoxocopper(II) Complex: Probing the Link between Coordination Number and Reactivity.

Although the reactivity of five-coordinate end-on superoxocopper(II) complexes, CuII(η1-O2•-), is dominated by hydrogen atom transfer, the majority of four-coordinate CuII(η1-O2•-) complexes published thus far display nucleophilic reactivity. To investigate the origin of this difference, we have developed a four-coordinate end-on superoxocopper(II) complex supported by a sterically encumbered bis(2-pyridylmethyl)amine ligand, dpb2-MeBPA (1), and compared its substrate reactivity with that of a five-coordinate end-on superoxocopper(II) complex ligated by a similarly substituted tris(2-pyridylmethyl)amine, dpb3-TMPA (2). Kinetic isotope effect (KIE) measurements and correlation of second-order rate constants (k2's) versus oxidation potentials (Eox) for a range of phenols indicates that the complex [CuII(η1-O2•-)(1)]+ reacts with phenols via a similar hydrogen atom transfer (HAT) mechanism to [CuII(η1-O2•-)(2)]+. However, [CuII(η1-O2•-)(1)]+ performs HAT much more quickly, with its k2 for reaction with 2,6-di-tert-butyl-4-methoxyphenol (MeO-ArOH) being >100 times greater. Furthermore, [CuII(η1-O2•-)(1)]+ can oxidize C-H bond substrates possessing stronger bonds than [CuII(η1-O2•-)(2)]+ is able to, and it reacts with N-methyl-9,10-dihydroacridine (MeAcrH2) approximately 200 times faster. The much greater facility for substrate oxidation displayed by [CuII(η1-O2•-)(1)]+ is attributed to it possessing higher inherent electrophilicity than [CuII(η1-O2•-)(2)]+, which is a direct consequence of its lower coordination number. These observations are of relevance to enzymes in which four-coordinate end-on superoxocopper(II) intermediates, rather than their five-coordinate congeners, are routinely invoked as the active oxidants responsible for substrate oxidation.

Sterically Stabilized End-On Superoxocopper(II) Complexes and Mechanistic Insights into Their Reactivity with O-H, N-H, and C-H Substrates.

Instability of end-on superoxocopper(II) complexes, with respect to conversion to peroxo-bridged dicopper(II) complexes, has largely constrained their study to very low temperatures. This limits their kinetic capacity to oxidize substrates. In response, we have developed a series of bulky ligands, Ar3-TMPA (Ar = tpb, dpb, dtbpb), and used them to support copper(I) complexes that react with O2 to yield [CuII(η1-O2•-)(Ar3-TMPA)]+ species, which are stable against dimerization at all temperatures. Binding of O2 saturates at subambient temperatures and can be reversed by warming. The onset of oxygenation for the Ar = tpb and dpb systems is observed at 25 °C, and all three [CuII(η1-O2•-)(Ar3-TMPA)]+ complexes are stable against self-decay at temperatures of ≤-20 °C. This provides a wide temperature window for study of these complexes, which was exploited by performing extensive reaction kinetics measurements for [CuII(η1-O2•-)(tpb3-TMPA)]+ using a broad range of O-H, N-H, and C-H bond substrates. This includes correlation of second order rate constants (k2) versus oxidation potentials (Eox) for a range of phenols, construction of Eyring plots, and temperature-dependent kinetic isotope effect (KIE) measurements. The data obtained indicate that reaction with all substrates proceeds via H atom transfer (HAT), reaction with the phenols proceeds with significant charge transfer, and full tunneling of both H and D atoms occurs in the case of 1,2-diphenylhydrazine and 4-methoxy-2,6-di-tert-butylphenol. Oxidation of C-H bonds proved to be kinetically challenging, and whereas [CuII(η1-O2•-)(tpb3-TMPA)]+ can oxidize moderately strong O-H and N-H bonds, it is only able to oxidize very weak C-H bonds.

An Azomethine-H-Based Fluorogenic Sensor for Formic Acid.

Formic acid (FA) is an important C1-containing feedstock that serves as a masked source of dihydrogen gas (H2). To encourage the adoption of cleaner (noncarbonaceous) energy sources, FA detection and sensing is thus of considerable interest. Here, we examine the use of a commercially available dye, azomethine-H (Az-H), for FA sensing. Solution studies confirm that FA quenches both the absorbance and the luminescence properties of Az-H. FA was additionally found to attenuate a known Az-H (E)-to-(Z) conformational change, suggesting an Az-H/FA interaction, possibly through hydrogen bonding; this phenomenon was probed using 1H NMR spectroscopy. Moving toward a solid-state sensor, the Az-H probe was incorporated into a gelatin-based matrix. On exposure to FA, the luminescence of this system was found to increase in a FA-dependent manner, attributed to the formation of stable hydrogen-bonded structures, facilitating a (Z)-to-(E) isomerization via imine protonation, allowing for production of the more luminescent (E)-isomer. This fluorogenic signal was used as a FA sensor with an estimated detection limit of ca. 0.4 ppb FA vapor. This work constitutes an important step toward a highly sensitive FA sensor in both the solution and solid state, opening new space for the detection of organic acids in differing chemical environments.

Healable, Recyclable, and Programmable Shape Memory Organogels Based on Highly Malleable Catalyst-Free Carboxylate Linkages.

The development of healable and recyclable organogels possessing responsive abilities is mainly hindered by the unavailability of many dynamic covalent linkages that undergo exchange reaction below the boiling temperature of organic swelling medium. Furthermore, the exchange is desired to be effective under catalyst-free conditions to circumvent the issue of catalyst leaching during the swelling process. Especially, imparting swift reversibility to thermostable carboxylate linkages is challenging. In this approach, we have utilized the ß-keto anchimeric assistance as the tool to induce swift reversibility into the conventional carboxylate linkage under mild temperature (∼70-90 °C) and catalyst-free conditions. Using this ß-keto carboxylate linkage as an associative bond exchange mean, strong (tensile strength = 0.3 MPa) and stretchable (ultimate elongation ≈ 600%) covalent adaptable organogels (CAOs) with anisotropic swelling, remoldable, self-healing, and shape memory ability are derived from commercially available precursors. The shape memory ability of these samples shows dependency on the shape fixing time and can be programmed, targeting further applications. Soft actuators may be fabricated from the CAOs using temperature and solvent as the activating tools. This research demonstrates that the conventional carboxylate linkages can be made labile under mild conditions for further applications.

CFD and Optimization Study of Frictional Pressure Drop Through Bends.

BACKGROUND: The non-Newtonian pseudoplastic liquid flow through different types of the bend is more complicated compared to the simple straight pipe as the bends are associated with various curve geometry. Bends have wide application in bioengineering, biotechnology and biomedical such as study biofluids, blood rheology study, the design of medical equipment like equipment measuring the cholesterol etc. Method: The papers deal with the estimation of loss coefficient and frictional pressure drop of Newtonian and non-Newtonian pseudoplastic fluid flow through the different bend of 0.0127 m diameter pipe geometry using commercially available CFD software fluent 6.3. We revised all patents relating to the pipe flow through different types of bend. The present study also deals with the efficient application of Genetic Algorithm (GA) for optimization of frictional pressure drop. Laminar Non-Newtonian Power law model is used for Sodium Carboxy Methyl Cellulose (SCMC) solution to solve the continuity and the momentum equations numerically. Generalized input-output correlation has been developed by Gene Expression Programming (GEP) using Matlab. RESULTS: The above-mentioned algorithm is used to predict and optimize the pressure drop. It has been found that, the process exhibit the minimum pressure drop across the bend under optimum condition (Angle = 133.160, Concentration = 0.2 Kg/m3 and velocity = 0.53 m/s). The effect of flow rate, bend angle, fluid behaviour on static pressure and pressure drop has also been investigated. CONCLUSION: From the study, it can be concluded that the developed GA model has a good agreement with the CFD model. The software predicted data might be used to solve various industrial problems and also to design different equipment.

Synthesis and coordination chemistry of new asymmetric donor/acceptor pincer ligands, 1,3-C6H4(CH2PtBu(Rf))2 (Rf = CF3, C2F5).

Syntheses of new asymmetric pincer precursors 1,3-C6H4{CH2P(tBu,X)}2 (tBu,XPCPH; X = Cl, SiMe3, OPh) and a new class of hybrid donor/acceptor pincer ligands 1,3-C6H4{CH2P(tBu,Rf)}2 (tBu,RfPCPH; Rf = CF3, C2F5) are reported. All tBu,XPCPH compounds are obtained as mixtures of meso and rac diastereomers in varying ratios (meso : rac ∼ 4 : 1 to 3 : 2) which were used without separation. Treatment of Ru(cot)(cod) with tBu,CF3PCPH under 1 atm H2 in acetone at 20 °C produced the hydride solvate (tBu,CF3PCP)Ru(acetone)xH which was not isolated, but could be trapped as stable diene complexes (tBu,CF3PCP)Ru(L)2H (L2 = cod (1[combining low line]), nbd (2[combining low line])). Catalytic cyclooctane dehydrogenation studies demonstrate that 2[combining low line] has ∼50% the activity of (CF3PCP)Ru(cod)(H), but significantly higher catalyst stability and is able to operate at higher catalyst loading concentrations without deactivation via bimolecular decomposition.

Dye-Labeled Polyacryloyl Hydrazide-Ag Nanoparticle Fluorescent Probe for Ultrasensitive and Selective Detection of Au Ion.

The efficiency of a fluorescence sensing device based on metal-enhanced fluorescence (MEF) is dependent on the optimization of interaction between the fluorophore and the metal nanoparticle (NP). Herewith, ultrasensitive and selective turn-on sensing of Au3+ is achieved by using a suitable combination of fluorophore and metal NP system through sequential MEF effect. Dansyl hydrazide-tagged Ag NPs in the polyacryloyl hydrazide cavity are utilized to sense the picomolar concentration of Au3+ in aqueous media. We demonstrated that the selective Au3+ sensing is due to the selective deposition of Au on the Ag NP surface over the 16 other metal ions studied. The sensitivity is assigned to the strong overlapping of the emission band of the fluorophore with the surface plasmon band of the Au and improvement of fluorescence signal through successive MEF by Ag and Au colloids. The sensing is associated with a fivefold increase in fluorescence intensity and appearance of violet color of the solution. These luminescent Ag-Au bimetallic NPs may be utilized to trace cancer cells in biological systems and for cell imaging applications.