Metal Complexes of Singly,Doubly and Triply Linked Porphyrins and Corroles: An Insight into the Physicochemical Properties

Metal complexes of multi-porphyrins and multi-corroles are unique systems that display a host of extremely interesting properties. Availability of free meso and β positions allow formation of different types of directly linked bis-porphyrins giving rise to intriguing optical and electronic properties. While the fields of metalloporphyrin and corroles monomer have seen exponential growth in the last decades, the chemistry of metal complexes of bis-porphyrins and bis-corroles remain rather underexplored. Therefore, the impact of covalent linkages on the optical, electronic, (spectro)electrochemical, magnetic and electrocatalytic activities of metal complexes of bis-porphyrins and -corroles has been summarized in this review article. This article shows that despite the (still) somewhat difficult synthetic access to these molecules, their extremely exciting properties do make a strong case for pursuing research on these classes of compounds.     

Variable electron-phonon coupling in isolated metallic carbon nanotubes observed by Raman scattering

We report the existence of broad and weakly asymmetric features in the high-energy (G) Raman modes of freely suspended metallic carbon nanotubes of defined chiral index. A significant variation in peak width (from 12 cm(-1) to 110 cm(-1)) is observed as a function of the nanotube's chiral structure. When the nanotubes are electrostatically gated, the peak widths decrease. The broadness of the Raman features is understood as the consequence of coupling of the phonon to electron-hole pairs, the strength of which varies with the nanotube chiral index and the position of the Fermi energy.     

Slow light in bacteriorhodopsin solution using coherent population oscillations

Slow light is demonstrated in liquid phase in an aqueous bacteriorhodopsin (bR) solution at room temperature. Group velocity as low as 3 m/s (all the way to c) is achieved by exploiting the photoisomerization property of bR for coherent population oscillations. Slow light in the liquid phase offers several advantages over solids or vapors for a variety of applications: (i) shorter lifetimes of the M state facilitate slow light at higher modulation frequencies, (ii) convection makes it possible to obtain large signal delays even at high input powers, and (iii) solution concentration is another convenient parameter to vary the signal delay over a wide range.     

Chemical Composition and Antioxidant Activity of the Leaf Essential Oil of Schefflera venulosa

Chemistry of Natural Compounds -     

Directed Design of a AuI Complex with a Reduced Mesoionic Carbene Radical Ligand: Insights from 1,2,3-Triazolylidene Selenium Adducts and Extensive Electrochemical Investigations

Carbene-based radicals are important for both fundamental and applied chemical research. Herein, extensive electrochemical investigations of nine different 1,2,3-triazolylidene selenium adducts are reported. It is found that the half-wave potentials of the first reduction of the selones correlate with their calculated LUMO levels and the LUMO levels of the corresponding triazolylidene-based mesoionic carbenes (MICs). Furthermore, unexpected quasi-reversibility of the reduction of two triazoline selones, exhibiting comparable reduction potentials, was discovered. Through UV/Vis/NIR and EPR spectroelectrochemical investigations supported by DFT calculations, the radical anion was unambiguously assigned to be triazoline centered. This electrochemical behavior was transferred to a triazolylidene-type MIC-gold phenyl complex resulting in a MIC-radical coordinated Au^I species. Apart from UV-Vis-NIR and EPR spectroelectrochemical investigations of the reduction, the reduced gold-coordinated MIC radical complex was also formed in situ in the bulk through chemical reduction. This is the first report of a monodentate triazolylidene-based MIC ligand that can be reduced to its anion radical in a metal complex. The results presented here provide design principles for stabilizing radicals based on MICs.     

Rapid Characterization of Molecular Diffusion by NMR Spectroscopy

An NMR‐based approach for rapid characterization of translational diffusion of molecules has been developed. Unlike the conventional method of acquiring a series of 2D ¹³C and ¹H spectra, the proposed approach involves a single 2D NMR spectrum, which can be acquired in minutes. Using this method, it was possible to detect the presence of intermediate oligomeric species of diphenylalanine in solution during the process of its self‐assembly to form nanotubular structures.     

Palladium‐Catalyzed Oxidative Carbocyclization–Carbonylation of Allenynes and Enallenes

A highly efficient oxidative carbocyclization–carbonylation reaction cascade of allenynes and enallenes has been developed using a Pd^II salt in low catalytic amounts under ambient temperature and pressure (1 atm of carbon monoxide). The use of DMSO as an additive was found to be important for an efficient reaction. A wide range of alcohols as trapping reagents were used to give the corresponding esters in good yields.     

Design and Development of Ultrafast Sinapic Acid Sensor Based on Electrochemically Nanotuned Gold Nanoparticles and Solvothermally Reduced Graphene Oxide

We report for the first time sinapic acid (SA) sensing based on nanocomposite comprising electrochemically tuned gold nanoparticles (EAuNPs) and solvothermally reduced graphene oxide (rGO). The synthesized EAuNPs, rGO, and EAuNPs‐rGO nanocomposite were characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), particle size analysis, and Raman spectroscopy. A proof‐of‐concept electrochemical sensor for SA was developed based on synthesized EAuNPs‐rGO nanocomposite, which was characterized by electrochemical techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The developed sensor detected SA with a linear dynamic range (LDR) between 20 μM and 200 μM and detection limit (DL) of 33.43 (±0.21) nM (RSD<3.32 %). To show the useful purpose of the sensor probe in clinical applications, SA was detected in human urine samples, which showed the percentage recovery between 82.6 % and 92.8 %. Interferences due to various molecules such as L‐cystine, glycine, alanine, serum albumin, uric acid, citric acid, ascorbic acid, and urea were tested. Long‐term stability of the sensor probe was examined, which was found to be stable up to 6 weeks. The sensor fabricated using EAuNPs‐rGO nanocomposite has many attractive features such as; simplicity, rapidity, and label‐free detection; hence, it could be a method of choice for SA detection in various matrices.     

How well does molecular simulation reproduce environment-specific conformations of the intrinsically disordered peptides PLP,TP2 and ONEG?

Understanding the conformational ensembles of intrinsically disordered proteins and peptides (IDPs) in their various biological environments is essential for understanding their mechanisms and functional roles in the proteome, leading to a greater knowledge of, and potential treatments for, a broad range of diseases. To determine whether molecular simulation is able to generate accurate conformational ensembles of IDPs, we explore the structural landscape of the PLP peptide (an intrinsically disordered region of the proteolipid membrane protein) in aqueous and membrane-mimicking solvents, using replica exchange with solute scaling (REST2), and examine the ability of four force fields (ff14SB, ff14IDPSFF, CHARMM36 and CHARMM36m) to reproduce literature circular dichroism (CD) data. Results from variable temperature (VT) ¹H and Rotating frame Overhauser Effect SpectroscopY (ROESY) nuclear magnetic resonance (NMR) experiments are also presented and are consistent with the structural observations obtained from the simulations and CD. We also apply the optimum simulation protocol to TP2 and ONEG (a cell-penetrating peptide (CPP) and a negative control peptide, respectively) to gain insight into the structural differences that may account for the observed difference in their membrane-penetrating abilities. Of the tested force fields, we find that CHARMM36 and CHARMM36m are best suited to the study of IDPs, and accurately predict a disordered to helical conformational transition of the PLP peptide accompanying the change from aqueous to membrane-mimicking solvents. We also identify an α-helical structure of TP2 in the membrane-mimicking solvents and provide a discussion of the mechanistic implications of this observation with reference to the previous literature on the peptide. From these results, we recommend the use of CHARMM36m with the REST2 protocol for the study of environment-specific IDP conformations. We believe that the simulation protocol will allow the study of a broad range of IDPs that undergo conformational transitions in different biological environments.

A protocol for simulating intrinsically disordered peptides in aqueous and hydrophobic solvents is proposed. Results from four force fields are compared with experiment. CHARMM36m performs the best for the simulated IDPs in all environments.     

Effect of grinding on the low temperature photoluminescence of certain inorganic crystals

The broadening as well as shift in the photoluminescence spectra of K₂[Pt(CN)₄] · 3 H₂O, Ba[Pt(CN)₄] · 4 H₂O, CdS:Te and Ru(C₁₅H₁₁N₃)₂I₂ · H₂O crystals take place with their grinding. The original vibronic peaks at 632 and 628 nm of CdS:Te and Ru(C₁₅H₁₁N₃)₂I₂ · H₂O crystals, respectively, disappear with the grinding. A new vibronic peak at 650 nm appears with grinding of Ru(C₁₅H₁₁N₃)₂I₂ · H₂O crystals. It is concluded that the change in the photoluminescence spectra is attributed to the creation of dislocations during the process of grinding.