Synthesis of Cu–Cr diketo,sublimable, eutectic composite complex,rod crystals from LDH as suitable MOCVD precursor of CuCr2O4 catalysts upon ceramic preforms for N2O decomposition

Metal-acteylacetonates are important sublimable metal-organic precursors for metal-oxide thin film formation over solid preforms by MOCVD (Metal Organic Chemical Vapour Deposition) technique. Mixed-metal-acetylacetonates (MMAA) are suitable starting materials for mixed metal nano-oxidic thin film formation through such facile routes. Layered Double Hydroxides (LDH) of suitable metal ion combination can perform as appropriate starting base for neutralisation by enol form of 2,4-pentanedione or acteylacetonate tautomer ligands to obtain such MMAA. In this paper synthesis of composite crystals of Cu(II)/Cr(III) acetylacetonates (CCAA) is reported by the reaction of Cu–Cr-LDH with acetylacetone. The products were characterized by various different techniques. The surface area and pore volume analysis of the crystals showed the formation of nanopores in the compound. TEM analysis confirmed that the inner core of the nanoporous crystals of Cu(acac)₂ was covered by coating of poorly crystallised Cr(acac)₃ and they together form the composite crystals, and they together form the composite crystals. Due to eutectic mixture formation the melting point of CCAA lies in between the melting points of individual components Cu(acac)₂ and Cr(acac)₃ and shows sublimability, a property important for the formation of MOCVD films. The composite was used for CuCr₂O₄ spinel mixed oxide films formation over solid ceramic honeycomb monolithic substrates. Application prospects of the route in the field of catalysis is high as it can directly combine the benefits of mixed metal oxide catalysis and structured supports without the involvement of a third component. In this work the performance of such a catalytic device has been tested for low temperature decomposition of high Global Warming Potential (GWP) gas N₂O to N₂ and O₂.     

Characteristic behaviour of plasma fluctuations inside a plasma bubble in presence of a magnetic field due to the formation of a potential well

Experiments were carried out to observe the effect of a magnetic field and grid biasing voltage in presence of a plasma bubble in a magnetized, filamentary discharge plasma system. A spherical mesh grid of 80% optical transparency was negatively biased and introduced into the plasma for creating a plasma bubble. Diagnostics via an electrical Langmuir probe and a hot emissive probe were extensively used for scanning the plasma bubble. Plasma floating potential fluctuations were measured at three different positions of the plasma bubble. The instability in the pattern showed the dynamic transition from periodic to chaotic for increasing magnetic fields. Time scale analysis using continuous wavelet transform was carried out to identify the presence of non‐linearity from the contour plots. The mechanisms of the low‐frequency instabilities along with the transition to chaos could be qualitatively explained. Non‐linear techniques such as fast Fourier transform, phase space plot, and recurrence plot were used to explore the dynamics of the system appearing during plasma fluctuations. In order to demonstrate the observed chaotic phenomena in this study, characteristics of chaos such as the Lyapunov exponent were obtained from experimental time series data. The experimentally observed potential structure is confirmed with numerical analysis based on fluid hydrodynamics.     

Oriented Crystallization on Organic Monolayers to Control Concomitant Polymorphism

Nucleation events and crystal growth can be guided by molecular recognition at interfaces through intermolecular interactions. The short-acting antimicrobial sulfa drug sulfathiazole is known for its concomitant crystallization, which has five known polymorphs, due to conformational flexibility and hydrogen-bond synthon variation. In its development stage of a drug the issue of concomitant crystallization needs to be addressed with respect to patent litigation, including legal actions to protect patents against infringement. A functional self-assembled monolayer (SAM) of organic thiol on a gold surface has been employed as an efficient approach to control concomitant nucleation of such flexible drugs. The crystallization on a SAM surface is mostly kinetically driven and often leads to the nucleation of novel metastable forms. Spectroscopic, thermal analysis and X-ray diffraction studies reveal that a previously unknown, sixth form of the drug nucleates on the designed SAM surface.     

Perturbing π-clouds with Substituents to Study the Effects on Reaction Dynamics of gauche-1,3-Butadiene to Bicyclobutane Electrocyclization

The conical intersection (CI) governs the ultra-fast relaxation of excited states in a radiationless manner and are observed mainly in photochemical processes. In the current work, we investigated the effects of substituents on the reaction dynamics for the conversion of gauche-1,3-butadiene to bicyclobutane via photochemical electrocyclization. We incorporated both electron withdrawing (−F) and donating (−CH₃) groups in the conjugated system. In our study, we optimized the minimum energy conical intersection (MECI) geometries using the multi-configurational state-averaged CASSCF approach, whereas, to study the ground state reaction pathways for the substituted derivatives, dispersion corrected, B3LYP-D3 functional was used. The non-adiabatic surface hopping molecular dynamics simulations were performed to observe the behaviour of electronic states involved throughout the photoconversion process. The results obtained from the multi-reference second-order perturbation correction of energy at the XMS-CASPT2 level of theory, topography analysis, and non-adiabatic dynamics suggest that the −CH₃ substituted derivatives can undergo faster thermal conversion to the product in the ground state with a smaller activation energy barrier compared to −F substituted derivative. Our study also reveals that the GBUT to BIBUT conversion follows both conrotatory and disrotatory pathways, whereas, on substitution with −F or −CH₃, the conversion proceeds via the conrotatory pathway.     

Reversed‐phase liquid chromatography with electrospray mass detection and 1H and 13C NMR characterization of new process‐related impurities,including forced degradants of Efavirenz: Related substances correlated to the synthetic pathway

In this study, a stability‐indicating reversed‐phase liquid chromatographic electrospray mass spectrometric method was developed and validated for the determination of process‐related impurities and forced degradants of Efavirenz in bulk drugs. Efavirenz was subjected to acid, alkaline hydrolysis, H₂O₂ oxidation, photolysis, and thermal stress. Significant degradation was observed during alkaline hydrolysis, and the degradants were isolated on a mass‐based purification system and characterized by high‐resolution mass spectrometry, positive electrospray ionization tandem mass spectrometry, and ¹H and ¹³C NMR spectroscopy. Accurate mass measurement and NMR spectroscopy revealed the possible structure of process‐related impurities and degradant under stress conditions. The acceptable separation was accomplished on Waters bondapak C₁₈ column (250 mm × 4.6 mm; 5 μm), using 5 mM ammonium acetate and acetonitrile as a mobile phase in a gradient elution mode at a flow rate of 1.0 mL/min. The eluents were monitored by diode array detector at 247 nm and quantitation limits were obtained in the range of 0.1–2.5 μg/mL for Efavirenz, degradants, and process‐related impurities. The liquid chromatography method was validated with respect to accuracy, precision, linearity, robustness, and limits of detection and quantification as per International Conference on Harmonization guidelines.     

Interaction of thermal radiation with laminar natural convection from a horizontal cylinder in air

The heat transfer rates from a horizontal cylindrical surface of an internally heated tube under constant heat flux conditions are evaluated with the aid of integral analysis giving due consideration to both natural convection and thermal radiation to ambient medium of air. It is observed that non-isothermal conditions around the periphery of the tube arise due to the conjugate effects of the three modes of energy transmission viz., conduction, convection and radiation. The theoretical analysis is further validated with the experimental results and the coincidence is found to be very satisfactory.Die Wärmeübertragungsraten einer horizontalen zylindrischen Oberfläche eines innen erwärmten Rohres mit konstantem Wärmestrom sind mit Hilfe von Integralrechnungen berechnet worden, die sich auf die freie Konvektion und thermische Strahlung mit Luft als Umgebungsmedium beziehen. Es ist beobachtet worden, daß nicht-isotherme Bedingungen am Umfang des Rohres aus den drei Energieübertragungsarten Leitung, Konvektion und Strahlung entstehen. Die theoretische Berechnung wurde mit experimentellen Ergebnissen bestätigt und die Koinzidenz stellte sich als sehr zufriedenstellend heraus.