Photoinduced dynamics of a cyanine dye: parallel pathways of non-radiative deactivation involving multiple excited-state twisted transients

Cyanine dyes are broadly used for fluorescence imaging and other photonic applications. 3,3′-Diethylthiacyanine (THIA) is a cyanine dye composed of two identical aromatic heterocyclic moieties linked with a single methine, –CH. The torsional degrees of freedom around the methine bonds provide routes for non-radiative decay, responsible for the inherently low fluorescence quantum yields. Using transient absorption spectroscopy, we determined that upon photoexcitation, the excited state relaxes along two parallel pathways producing three excited-state transients that undergo internal conversion to the ground state. The media viscosity impedes the molecular modes of ring rotation and preferentially affects one of the pathways of non-radiative decay, exerting a dominant effect on the emission properties of THIA. Concurrently, the polarity affects the energy of the transients involved in the decay pathways and further modulates the kinetics of non-radiative deactivation.     

Development of Polar Organic Mode Chromatographic Method by Polysaccharide-Based Immobilized Chiral Selector and Validation for the Determination of the Enantiopurity of Novel Mineralocorticoid Receptor Antagonist Atropisomer–Esaxerenone

Esaxerenone is a new nonsteroidal mineralocorticoid receptor antagonist utilized to treat high blood pressure. Chemically, esaxerenone is a pyrrole derivative consisting of hindered rotation, which results in stereoisomers named atropisomers. Currently, no methods exist for the separation and quantification of these atropisomers. A new and accurate chiral liquid chromatographic technique was developed and validated to estimate the enantiomeric purity of esaxerenone. Polar organic chiral separation was carried out on an immobilized amylose-based chiral stationary phase (Chiralpak IG) with methanol:acetonitrile:diethylamine (9:1:0.1, v/v/v) mixture as a mobile phase. The total runtime was 15 min, and the resolution (R_s) between the atropisomers was more than 3.0. The detection and quantification thresholds for the R-atropisomer were found to be 0.03 and 0.1 µg mL^?1, respectively, for a test concentration of esaxerenone (1000 µg mL^?1). Over the range from the limit of quantification to 0.3 percent, the method's linearity for the R-atropisomer was excellent (R²?>?0.999). The R-atropisomer recovery varied from 95 to 102%, confirming the method’s good accuracy. For a 48-h research period, the chemical was shown to be stable.

     

Synthesis and conformational studies of peptides from new C-linked carbo-beta-amino acids (beta-Caas) with anomeric methylamino- and difluorophenyl moieties

New C-linked carbo-beta-amino acids (beta-Caas), Cbz-(S)-beta-Caa-(NHBoc)-OMe (1) and Cbz-(R)-beta-Caa-(NHBoc)-OMe (2), with an additional amine group (methylamino group of NHBoc) at the C-1 position of the lyxofuranoside side chain and Boc-(S)-beta-Caa-(diFP)-OMe (3) and Boc-(R)-beta-Caa-(diFP)-OMe (4), with a C-difluorophenyl (diFP) moiety at the anomeric position of the lyxofuranoside side chain were prepared from D-mannose. Beta-peptides [tetra- and hexapeptides] were synthesized from these beta-Caas, 'epimeric' [at the amine stereocentre (C(beta))], using the concept of 'alternating chirality' to carry out their conformational studies [NMR (CDCl(3)), CD and MD]. In the monomer design, it was envisaged that the presence of an additional amine group in 1 or 2 would help in solubilizing the peptides in water, while, the C-difluorophenyl (diFP) moiety of 3 and 4 is expected to enhance the biological activity. The peptides having 1 and 2, though could not retain their 12-10-mixed helices in water, have shown moderate activity against gram positive and gram negative bacterial strains. The peptides prepared from 3 and 4, much against our expectations, did not display any biological activity.     

Surfactant-Mediated and Morphology-Controlled Nanostructured LiFePO4/Carbon Composite as a Promising Cathode Material for Li-Ion Batteries

The synthesis of morphology-controlled carbon-coated nanostructured LiFePO₄ (LFP/Carbon) cathode materials by surfactant-assisted hydrothermal method using block copolymers is reported. The resulting nanocrystalline high surface area materials were coated with carbon and designated as LFP/C123 and LFP/C311. All the materials were systematically characterized by various analytical, spectroscopic and imaging techniques. The reverse structure of the surfactant Pluronic® 31R1 (PPO-PEO-PPO) in comparison to Pluronic® P123 (PEO-PPO-PEO) played a vital role in controlling the particle size and morphology which in turn ameliorate the electrochemical performance in terms of reversible specific capacity (163 mAh g⁻¹ and 140 mAh g⁻¹ at 0.1 C for LFP/C311 and LFP/C123, respectively). In addition, LFP/C311 demonstrated excellent electrochemical performance including lower charge transfer resistance (146.3 Ω) and excellent cycling stability (95 % capacity retention at 1 C after 100 cycles) and high rate capability (163.2 mAh g⁻¹ at 0.1 C; 147.1 mAh g⁻¹ at 1 C). The better performance of the former is attributed to LFP nanoparticles (<50 nm) with a specific spindle-shaped morphology. Further, we have also evaluated the electrode performance with the use of both PVDF and CMC binders employed for the electrode fabrication.     

Catalytic Conversion of Glucose into Levulinic Acid Using 2-Phenyl-2-Imidazoline Based Ionic Liquid Catalyst

Levulinic acid (LA) is an industrially important product that can be catalytically valorized into important value-added chemicals. In this study, hydrothermal conversion of glucose into levulinic acid was attempted using Brønsted acidic ionic liquid catalyst synthesized using 2-phenyl-2-imidazoline, and 2-phenyl-2-imidazoline-based ionic liquid catalyst used in this study was synthesized in the laboratory using different anions (NO₃, H₂PO₄, and Cl) and characterized using ¹H NMR, TGA, and FT-IR spectroscopic techniques. The activity trend of the Brønsted acidic ionic liquid catalysts synthesized in the laboratory was found in the following order: [C₄SO₃HPhim][Cl] > [C₄SO₃HPhim][NO₃] > [C₄SO₃HPhim][H₂PO₄]. A maximum 63% yield of the levulinic acid was obtained with 98% glucose conversion at 180 °C and 3 h reaction time using [C₄SO₃HPhim][Cl] ionic liquid catalyst. The effect of different reaction conditions such as reaction time, temperature, ionic liquid catalyst structures, catalyst amount, and solvents on the LA yield were investigated. Reusability of [C₄SO₃HPhim][Cl] catalyst up to four cycles was observed. This study demonstrates the potential of the 2-phenyl-2-imidazoline-based ionic liquid for the conversion of glucose into the important platform chemical levulinic acid.     

Two new macrocyclic diaryl ether heptanoids from Boswellia ovalifoliolata

The stems of Boswellia ovalifoliolata BAL. & HENRY (Burseraceae) afforded two new macrocyclic diaryl ether heptanoids, ovalifoliolatin A (1) and B (2) together with three known compounds; acerogenin C (3), 3 alpha-hydroxyurs-12-ene (4), and sitost-4-en-3-one (5). The structures were established by means of spectroscopic analysis and compounds 1, 3-5 were evaluated for their antibacterial activity.     

An unusual base-controlled equilibrium between monomeric and dimeric nickel(IV)–dimethylglyoxime complexes

Ionic nickel(IV)–dimethylglyoxime complexes have been prepared by oxidation of nickel(II)–dimethylglyoxime in alkaline solutions with ferricyanide. A novel base-controlled equilibrium is demonstrated between the monomeric and dimeric nickel(IV)–dimethylglyoxime complexes in solution. The oxidation state of nickel as +4 is confirmed by titration with hydroxylamine salt. The results obtained from the UV/VIS spectrophotometry, titrimetry, infrared and NMR studies are discussed.     

Effect of background derivatization on the signal enhancement of pesticide residues extracted from edible oils

The effect of background derivatization on the signal enhancement of pesticide residues extracted from edible oil samples was studied by GC with negative chemical ionization MS. The analytes were extracted by a solvent extraction process, and the extract was subjected to rapid low‐temperature fat precipitation. The residual fatty acids were silylated by derivatization with N,O‐bis(trimethylsilyl)trifluoroacetamide. The chromatograms obtained from the derivatized samples showed higher signal intensity and lower detection levels when compared to the direct analysis without derivatization. The sensitivity levels of the method are either better or comparable to that of previously reported methodologies. The LODs of the analyzed organochlorine, organophosphorus, and synthetic pyrethroid residues in sunflower, rice bran, and ground oil samples were in the range of 0.02–0.5 ng/g, and the LOQs were in the range of 0.1–2 ng/g. The intraday and interday accuracies were in the range of 81–116% with RSDs less than 14%. The recoveries obtained were in the range of 53–89% with the RSD values less than 13% for all the studied pesticide residues.     

Coatings of polyethylene glycol for suppressing adhesion between solid microspheres and flat surfaces

This article describes the development and the examination of surface coatings that suppress the adhesion between glass surfaces and polymer microspheres. Superparamagnetic doping allowed for exerting magnetic forces on the microbeads. The carboxyl functionalization of the polymer provided the means for coating the beads with polyethylene glycol (PEG) with different molecular weight. Under gravitational force, the microbeads settled on glass surfaces with similar polymer coatings. We examined the efficacy of removing the beads from the glass surfaces by applying a pulling force of ~1.2 pN. The percent beads remaining on the surface after applying the pulling force for approximately 5 s served as an indication of the adhesion propensity. Coating of PEG with molecular weight ranging between 3 and 10 kDa was essential for suppressing the adhesion. For the particular substrates, surface chemistry and aqueous media we used, coatings of 5 kDa manifested optimal suppression of adhesion: that is, only 3% of the microbeads remained on the surface after applying the pulling magnetic force. When either the glass or the beads were not PEGylated, the adhesion between them was substantial. Addition of a noncharged surfactant, TWEEN, above its critical micelle concentrations (CMCs) suppressed the adhesion between noncoated substrates. The extent of this surfactant-induced improvement of the adhesion suppression, however, did not exceed the quality of preventing the adhesion that we attained by PEGylating both substrates. In addition, the use of surfactants did not significantly improve the suppression of bead-surface adhesion when both substrates were PEGylated. These findings suggest that such surfactant additives tend to be redundant and that covalently grafted coatings of PEGs with selected chain lengths provide sufficient suppression of nonspecific interfacial interactions.