Synthesis and liquid crystalline properties of new amide‐modified poly(1,4‐cyclohexanedimethylene terephthalate)

New series of cycloaliphatic poly(ester‐amide)s, poly(1,4‐cyclohexanedimethyleneterephthalate‐co‐1,3‐cyclohexanedimethylene terephthalamide), were synthesized through solution polymerization route. The compositions of ester/amide units in the copolymers were varied from 0 to 100% by varying the amount of 1,4‐cyclohexanedimethanol and 1,3‐cyclohexanebis(methylamine) in the feed. The structures of the polymers were confirmed by NMR and FTIR, and the molecular weights were determined by inherent viscosity. The composition analysis by NMR reveals that the reactivity of the diamine toward the acid chlorides is lowered than that of diol, which results in the formation of more ester content in the poly (ester‐amides). The thermal analysis indicate that the new poly(ester‐amide)s having less than 10 mol % of amide linkages are thermotropic liquid crystalline from 200 to 250 °C and a thread like nematic phases are observed under the polarizing microscope. WXRD studies suggest that the liquid crystalline domains promote the nucleation process in the polyester chains and increases the percent crystallinity of the poly(ester‐amide)s. The glass transition temperature of the copolymers initially increases with increase in amide units because of the presence of nematic phases and subsequently follows the Flory–Fox behavior. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 42–52, 2006     

Combining synchronous fluorescence spectroscopy with multivariate methods for the analysis of petrol-kerosene mixtures

Synchronous fluorescence spectroscopy (SFS) is a rapid, sensitive and nondestructive method suitable for the analysis of multifluorophoric mixtures. The present study demonstrates the use of SFS and multivariate methods for the analysis of petroleum products which is a complex mixture of multiple fluorophores. Two multivariate techniques principal component regression (PCR) and partial least square regression (PLSR) have been successfully applied for the classification of petrol-kerosene mixtures. Calibration models were constructed using 35 samples and their validation was carried out with varying composition of petrol and kerosene in the calibration range. The results showed that the method could be used for the estimation of kerosene in kerosene-mixed petrol. The model was found to be sensitive, detecting even 1% contamination of kerosene in petrol.     

Thermodynamic Properties of Crystalline Cellulose Allomorphs Studied with Dispersion-Corrected Density Functional Methods

The phonon properties and thermodynamics of four crystalline cellulose allomorphs, Iα, Iβ, II, and III1, have been investigated using dispersion-corrected density functional theory (DFT). In line with experimental findings, the free energy differences between the studied cellulose allomorphs are small, less than 1 kJ/mol per atom. The calculated specific heat at constant volume (Cv) has been compared with the available experimental data in the temperature range 10–300 K. Quasiharmonic approximation has been employed to study thermodynamics and specific heat at constant pressure (Cp). For the studied temperature range of 10–400 K, the specific heat of all cellulose allomorphs shows very similar behavior. The calculated and experimental specific heat agree well at low temperatures below 100 K, but the deviation between theory and experiment increases with temperature. This may be due to increasing phonon anharmonicity as the temperature increases.     

From symmetry breaking to symmetry swapping: is Kasha's rule violated in multibranched phenyleneethynylenes?

The phenomenon of excited-state symmetry breaking is often observed in multipolar molecular systems, significantly affecting their photophysical and charge separation behavior. As a result of this phenomenon, the electronic excitation is partially localized in one of the molecular branches. However, the intrinsic structural and electronic factors that regulate excited-state symmetry breaking in multibranched systems have hardly been investigated. Herein, we explore these aspects by adopting a joint experimental and theoretical investigation for a class of phenyleneethynylenes, one of the most widely used molecular building blocks for optoelectronic applications. The large Stokes shifts observed for highly symmetric phenyleneethynylenes are explained by the presence of low-lying dark states, as also established by two-photon absorption measurements and TDDFT calculations. In spite of the presence of low-lying dark states, these systems show an intense fluorescence in striking contrast to Kasha''s rule. This intriguing behavior is explained in terms of a novel phenomenon, dubbed “symmetry swapping” that describes the inversion of the energy order of excited states, i.e., the swapping of excited states occurring as a consequence of symmetry breaking. Thus, symmetry swapping explains quite naturally the observation of an intense fluorescence emission in molecular systems whose lowest vertical excited state is a dark state. In short, symmetry swapping is observed in highly symmetric molecules having multiple degenerate or quasi-degenerate excited states that are prone to symmetry breaking.

Highly symmetric multibranched phenyleneethynylenes exhibit intense fluorescence despite the presence of low-lying dark states. The inversion of the energy order of excited states is explained in terms of a novel phenomenon dubbed “symmetry swapping”.     

Influence of divalent ions on composition and viscoelasticity of polyelectrolyte complexes

The addition of monovalent salts to polyelectrolyte complexes (PECs) comprising oppositely charged polyelectrolytes results in diminishing propensity for complexation, leading to complexes with higher water contents and lower moduli. However, the corresponding influence of multivalent ions on polyelectrolyte complexation has not yet been explored beyond enhanced screening effects. Here, we elucidate the significant impact of the valency of the salt cation on the composition, ion partitioning, and viscoelasticity of charge-matched PECs comprising sodium salt of poly(acrylic acid) and poly(allylamine hydrochloride). Notably, preferential partitioning of divalent cations (Ca²⁺ and Sr²⁺) into the complexes is observed, in stark contrast to the depletion of monovalent ions (Na⁺) from the complexes. Concomitantly, electrostatic bridging of polyanion chains by divalent ions is found to hinder their relaxation, manifesting as a non-monotonic evolution of the shear moduli of the complexes with increasing divalent salt concentrations. Relatedly, a failure of time-salt and time-ionic strength superposition approaches in presence of divalent ions is demonstrated, highlighting the nontrivial influence of these ions on chain relaxation behavior.     

Synthesis of enantiopure furo[2,3-b]pyrroles

A simple method for the preparation of enantiopure furo[2,3-b]pyrroles, a rare class of concave bicyclic nitrogen and oxygen heterocycle, in promising yield has been developed. The 3-substituted pyrrolidinediones prepared from (2S,3S)-tetrahydro-3-hydroxy-5-oxo-2,3-furandicarboxylic acid (Garcinia acid) have been cyclized diastereo as well as enantioselectively to furo[2,3-b]pyrroles. The cyclization follows Baldwin’s rule.     

Favipiravir (SARS-CoV-2) degradation impurities: Identification and route of degradation mechanism in the finished solid dosage form using LC/LC–MS method

Favipiravir finished dosage was approved for emergency use in many countries to treat SARS-CoV-2 patients. A specific, accurate, linear, robust, simple, and stability-indicating HPLC method was developed and validated for the determination of degradation impurities present in favipiravir film-coated tablets. The separation of all impurities was achieved from the stationary phase (Inert sustain AQ-C18, 250 × 4.6 mm, 5-μm particle) and mobile phase. Mobile phase A contained KH₂PO₄ buffer (pH 2.5 ± 0.05) and acetonitrile in the ratio of 98:2 (v/v), and mobile phase B contained water and acetonitrile in the ratio of 50:50 (v/v). The chromatographic conditions were optimized as follows: flow rate, 0.7 mL/min; UV detection, 210 nm; injection volume, 20 μL; and column temperature, 33°C. The proposed method was validated per the current International Conference on Harmonization Q2 (R1) guidelines. The recovery study and linearity ranges were established from the limit of quantification to 150% optimal concentrations. The method validation results were found to be between 98.6 and 106.2% for recovery and r² = 0.9995–0.9999 for linearity of all identified impurities. The method precision results were achieved below 5% of relative standard deviation. Forced degradation studies were performed in chemical and physical stress conditions. The compound was sensitive to chemical stress conditions. During the study, the analyte degraded and converted to unknown degradation impurities, and its molecular mass was found using the LC–MS technique and established degradation pathways supported by reaction of mechanism. The developed method was found to be suitable for routine analysis of research and development and quality control.     

Biogenic Synthesis of Rod Shaped ZnO Nanoparticles Using Red Paprika (Capsicum annuum L. var. grossum (L.) Sendt) and Their in Vitro Evaluation

Journal of Cluster Science - Metal oxide nanoparticles (NPs) have gained attention in biomedicine due to their broad spectrum of applications, such as targeted drug delivery, their use as...     

Ni0.1Co0.9Fe2O4-based electrochemical sensor for the detection of paracetamol

A novel electrochemical sensor based on nickel-doped cobalt ferrite nanoparticles (Ni_0.1Co_0.9Fe₂O₄)-modified glassy carbon electrode (NCF/GCE) was presented for the sensitive detection of paracetamol. Experimental conditions such as pH, applied potentials and concentration were investigated using cyclic voltammetric and chronoamperometric techniques. The modified electrode exhibited excellent catalytic response towards the oxidation of paracetamol with good reproducibility. The overpotential for oxidation of paracetamol is decreased, and the current response enhanced significantly on the modified electrode in comparison with that of bare electrode. Linear calibration curve is obtained over the range 2 μM to 8,000 μM having a detection limit of 11 nM. The modified electrode facilitated the simultaneous detection of paracetamol, ascorbic acid, and dopamine with good reproducibility.     

Dynamics of radionuclides activity,radon exhalation rate of soil and assessment of radiological parameters in the coastal regions of Kerala,India

Journal of Radioanalytical and Nuclear Chemistry - The activity concentration of natural radionucides such as 40K, 226Ra and 232Th and radon surface and mass exhalation rates of the soil were...