Ruthenium porphyrin functionalized single-walled carbon nanotube arrays--a step toward light harvesting antenna and multibit information storage

Ruthenium porphyrin functionalized single-walled carbon nanotube arrays have been prepared using coordination of the axial position of the metal ion onto 4-aminopyridine preassembled single-walled carbon nanotubes directly anchored to a silicon(100) surface (SWCNTs-Si). The formation of these ruthenium porphyrin functionalized single-walled carbon nanotube array electrodes (RuTPP-SWCNTs-Si) has been monitored using infrared spectroscopy (IR), differential pulse voltammetry (DPV), atomic force microscopy (AFM), laser desorption time-of-flight mass spectroscopy (LDI-TOF-MS), UV-vis spectroscopy, fluorescence spectroscopy, and cyclic voltammetry. Electrochemical results show two successive one-electron reversible redox waves. The surface concentration of the ruthenium porphyrin molecules is 3.44 x 10 (-8) mol cm (-2). Optical results indicate that the immobilization of ruthenium porphyrin enhances the light absorption of SWCNTs-Si surfaces in the visible light region. Moreover mixed assembly of ferrocene/porphyrin onto carbon nanotube arrays has been achieved by altering the ratio of two redox-active species in the deposition solution. These results suggest the ruthenium porphyrin modified electrodes are excellent candidates for molecular memory devices and light harvesting antennae.     

Ruthenium-Catalyzed Direct Reductive Amination of Carbonyl Compounds for the Synthesis of Amines: An Overview

Reductive amination is a valuable method for amine synthesis that has been the topic of a century‘s worth of in-depth study in both academia and industry. Amines and their derivatives serve as incredibly adaptable building blocks for a broad array of organic substrates and are significant precursors for a myriad of advanced chemicals, physiologically active compounds, agrochemicals, biomolecules, pharmaceuticals, and polymers. The creation of innovative catalytic processes for the long-term and selective synthesis of amines from readily accessible and environmentally benign reagents remains a top priority in chemical research. Both heterogeneous and homogeneous catalysts have been designed with success to enable these reactions to explore new amines. Ruthenium catalysts are employed in reductive amination owing to their stability, selectivity, versatility, low toxicity, and high efficiency. This review comprehensively overviews the Ru-catalyzed reductive amination processes and includes the literature from 2009 to 2022.     

Dual Chromophoric Meso-Aryl BODIPYs with Aggregation Induced Red-Emission Characteristics: Optical Properties and their Application in Fe3+ Detection

Herein, we report the design of meso-aryl BODIPYs as a structural motif for aggregation-caused quenching (ACQ) to aggregation-induced emission (AIE) transformation. A series of meso-aryl BODIPY derivatives were synthesized, by systematically increasing the size of the chromophore at the meso-position from phenyl to pyrene. The effect of various factors, such as the aryl ring size, solvents, viscosity, and metal cations, on the photophysical properties was analyzed. The emission properties are well correlated with the flexibility of the aromatic ring for free rotation around the C_aryl−C_BODIPY bond. Accordingly, meso-phenanthrene BODIPY ( PhB ) has the highest emission characteristics. The emission property of less bulky aryl-substituted BODIPYs increases by increasing the solvent viscosity. The interaction of Fe³⁺ ions with aryl-BODIPYs provides a prominent photophysical response based on Lewis-acid supported decomplexation of BF₂ in aryl-BODIPYs. The bichromophoric meso-aryl BODIPYs exhibit notable intramolecular excitation energy transfer from the aromatic ring to the BODIPY core, which is higher in meso-anthracene BODIPY( AB ). Hence, decorating BODIPYs with polycyclic aromatic systems generates a twisted structure, which inhibits the π-π stacking between the planar aromatic molecules. This can be proposed as an effective approach at the molecular level to convert planar aryl luminophores having ACQ to AIEgens. Besides, the meso-pyrene BODIPY derivative shows excellent mechanofluorochromic behaviour.     

Nanomolar Inhibitors for Two Distinct Biological Target Families from a Single Synthetic Sequence: A Next Step in Combinatorial Library Design?

One common synthetic route creates small-molecule libraries directed toward two functionally distinct target families. The novel structural template 1 can independently display the necessary pharmacophore patterns for inhibition of members of two different biomolecular target families, the matrix metalloproteinases (MMPs) or the phosphodiesterases (PDEs). The incorporation of multiple target family directed design elements into combinatorial library design could help expedite the pharmaceutical lead discovery process. Z=OR′ (PDE4), H (MMPs).     

Random minimal spanning tree and percolation on the N-cube

The N-cube is a graph with 2^N vertices and N2^N−1 edges. Suppose independent uniform random edge weights are assigned and let T be the spanning tree of minimal (total) weight. Then the weight of T is asymptotic to N⁻¹2^N ∑^∞_i=1 i⁻³ as N→∞. Asymptotics are also given for the local structure of T and for the distribution of its kth largest edge weight, k fixed. © 1998 John Wiley & Sons, Inc. Random Struct. Alg., 12, 63–82, 1998     

Pyrolysis of aminonitriles,cyanohydrazones, and cyanoacetamides. Part I. Elimination reaction of 1-arylmethyleneamino-1,2-dihydro-4,6-dimethyl-2-oxopyridine-3-carbonitriles and substituted benzaldehyde cyanoacetylhydrazones

Pyrolysis of the Schiff bases of 1-arylmethyleneamino-1,2-dihydro-4,6-dimethyl-2-oxopyridine-3-carbonitriles (1–5) has been studied. These compounds eliminate via a six-membered transition state to produce substituted benzonitriles and 2-hydroxy-4,6-dimethylpyridine-3-carbonitrile. These eliminations are unimolecular first-order reactions. The kinetic data gave a good correlation with σ⁰ values of the substituents on the aryl group with ρ = 0.83 at 520 K. Utilization of the pyrolytic reaction in synthesis of various benzonitriles is considered, and mechanistic information has been obtained by comparing the kinetic data and product analysis of the Schiff bases with their open-chain substituted benzaldehyde cyanoacetylhydrazones (6–9) analogues. © 1996 John Wiley & Sons, Inc.     

Integral invariants for non-barotropic flows in a four dimensional space time manifold

Properties of non-barotropic flows are described using Lie derivatives of differential forms in a Euclidean four dimensional space-time manifold. Vanishing of the Lie derivative implies that the corresponding physical quantity remains invariant along the integral curves of the flow. Integral invariants of non-barotropic perfect and viscous flows are studied using the concepts of relative and absolute invariance of forms. The four dimensional expressions for the rate of change of the generalized circulation, generalized vorticity flux, generalized helicity and generalized parity in the case of ideal and viscous non-barotropic flows are thereby obtained.     

Pyrene‐Functionalised,Alternating Copolyimide for Sensing Nitroaromatic Compounds

A novel, pyrene‐functionalised copolymer has been synthesised in a single step via imidisation of poly(maleic anhydride‐alt‐1‐octadecene) with 1‐pyrenemethylamine, and its potential for the detection of volatile nitro aromatic compounds (NACs) evaluated. The new copolymer forms complexes in solution with NACs such as 2,5‐dinitrobenzonitrile, as shown by ¹H NMR, UV‐vis and fluorescence spectroscopy. Moreover, thin films of this copolymer, cast from THF solution, undergo almost instantaneous fluorescence quenching when exposed to the vapour of 2,5‐dinitrobenzonitrile (a model for TNT) at ambient temperatures and pressures.