Simultaneous HPTLC-UV quantification of colchicine and gloriosine alkaloids in the natural population of Gloriosa superba L., collected from Eastern Ghats of India for the identification of elite chemotypes

Abstract

Intra-specific chemical variability in the natural population of Gloriosa superba from Eastern Ghats (India) was recorded through validated HPTLC method and in vitro antiarthritic activity of elite chemotypes was evaluated. In total, 36 population(s) of G. superba were mapped and, collected from the phytogeography and densitometric quantification through validated HPTLC-UV method revealed a significant (p?>?0.05) difference in the metabolite content of germplasm(s). Colchicine and gloriosine content varied from 0.005 to 0.275% and 0.003 to 0.119%, maximum was recorded in NBG-34 (Tirupati, Andhra Pradesh) and NBG-70 (Panchgani hill, Maharashtra) respectively. On cluster analysis, six chemotypes were selected for in vitro antiarthritic activity, although activity was not significantly different. The elite chemotype with highest metabolite(s) content did not exhibit the highest biological activity and thus suggests the synergistic action of extract toward the pharmacological activity. The study promotes the use of G. superba in herbal formulation development as an adjuvant therapy in gouty arthritis and will aid in site-specific exploration of elite chemotype(s) with validated pharmacological action to meet out the medicinal and commercial demands.     

2‐(4′‐Pyridyl‐N‐oxide)‐Substituted Hemithioindigos as Photoresponsive Guests for a Super Aryl‐Extended Calix[4]pyrrole Receptor

We report the synthesis of two 2‐(4′‐pyridyl‐N‐oxide)‐substituted hemithioindigos (HTIs). We probed their photoisomerization by using UV/Vis and ¹H NMR spectroscopy techniques. Light irradiation at λ=450 nm provoked the isomerization of the HTI Z isomer to the E counterpart to a large extent (≈80 % at the photostationary state). ¹H NMR titration experiments revealed the formation of thermodynamically and kinetically stable 1:1 inclusion complexes of the (Z)‐HTI isomers with a super aryl‐extended host (association constant>10⁴ m ^?1). Photoirradiation at λ=450 nm of the inclusion complexes induced the isomerization of the bound HTI N‐oxide to afford the (E)‐HTI?calix[4]pyrrole complex. We determined accurate association constant values for the 1:1 inclusion complexes of the (Z)‐ and (E)‐HTI isomers by using isothermal titration calorimetry experiments. The results showed that the stability constants of the (E)‐HTI complexes were 2.2–2.8‐fold lower than those of the (Z)‐HTI counterparts, which explains the lack of light‐induced release of the former to the bulk solution.     

Morita-Baylis-Hillman enal-based triple cascade strategy for anti-selective synthesis of highly functionalized tetrahydropyridines using iminium-enamine catalysis

A novel and efficient three-component coupling strategy for stereoselective synthesis of highly substituted tetrahydropyridines (THP) is reported in high yield (83–94%) with excellent diastereoselectivity (95–99%) in favor of anti-isomer. The reaction proceeds via sequential iminium-iminium-enamine mediated formation of three consecutive CC, CC and CN bonds in one-pot through reaction of [E]-α-cyano/nitro unsaturated aldehyde, activated methylene and aldimine/phenyl-N-tosyl-methanimine and opens up a new aspect for the utility of Morita-Baylis-Hillman (MBH) adducts in THP synthesis.     

Queueing and Fluid Analysis of Partial Message Discarding Policy

We consider a stream of packets that arrive at a queue with a finite buffer. A group of consecutive packets constitutes a frame. We assume that when an arriving packet finds the queue full, not only is the packet lost but also the future packets that belong to the same frame will be rejected. The first part of the paper deals with a detailed packet level queueing model; we obtain exact expressions for the stationary queue length distribution and the goodput ratio (i.e. the fraction of arriving frames that experience no losses). The second part deals with a fluid model and the fluid analysis leads to simple closed form expressions for the stationary workload process and the fluid goodput ratio.     

Synthesis and antitubercular activity evaluation of 4-furano-coumarins and 3-furano-chromones

The synthesis of novel 4-furano-coumarins and 3-furano-chromones has been achieved using silver-mediated oxidative C–H/C–H functionalization of 4-ethynylcoumarin/3-ethynylchromone with ethyl acetoacetate in 80%–90% and 82%–90% yields, respectively. The structure of the synthesized compounds was established on the basis of their spectral data analysis and the structure of one of the 4-furano-coumarins has been further confirmed on the basis of its X-ray crystallographic study. All eight synthesized 4-furano-coumarins and 3-furano-chromones exhibited moderate antitubercular activity against sensitive reference strain H37Rv of Mycobacterium tuberculosis.     

Effect of degradation on electronic properties of polymer solar cells

We present here the effect of degradation on electronic properties of polymer solar cells. Investigations were performed on two types of solar cells based on the bulk‐heterojunction network of poly(3‐hexylthiophene) and phenyl [6,6] C₆₁ butyric acid methyl ester, one with slow degradation whereas other with faster degradation. Samples were prepared in identical conditions with controlled atmosphere, but for faster degradation, one of the samples was exposed to ambient air (rich in O₂ and H₂O molecules) before deposition of top metal electrode. The sample with slow degradation showed linear degradation in short circuit current density (J_sc), whereas the sample with faster degradation exhibited exponential degradation in J_sc. Linear degradation happens due to degradation in the active layer only whereas the exponential degradation is because of through degradation of the solar cell. The effect of degradation is investigated on different diode parameters. Because of different degradation processes in the two samples, the variations in diode parameters with time are different. Copyright © 2013 John Wiley & Sons, Ltd.     

Copolymers of ethylene and sulfonated norbornene for proton exchange membranes

Terpolymers of ethylene, norbornene, and 5‐exo norbornene methyl alcohol are prepared using Pd phosphine sulfonates as catalysts. The pendant hydroxyl groups are then transformed into thioacetate groups. Films cast from the resulting polymers are then oxidized by hydrogen peroxide. This green oxidation method is found to quantitatively transform thioacetate groups into sulfonic acids, leading to the formation of sulfonated hydrocarbon ionomers. These ionomers are thermally stable, exhibit increasing conductivity up to 110 °C, and have a low water uptake, indicating that these materials are potentially interesting candidates for the preparation of fuel cell membranes. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2669–2676     

Synthesis of double perovskite and quadruple perovskite nanocrystals through post-synthetic transformation reactions

Lead-free halide perovskite nanocrystals (NCs) represent a group of emerging materials which hold promise for various optical and optoelectronic applications. Exploring facile synthetic methods for such materials has been of great interest to not only fundamental research but also technological implementations. Herein, we report a fundamentally new method to access lead-free Bi-based double perovskite (DP) and quadruple perovskite (or layered double perovskite, LDP) NCs based on a post-synthetic transformation reaction of Cs₃BiX₆ (X = Cl, Br) zero-dimensional (0D) perovskite NCs under mild conditions. The produced NCs show good particle uniformity, high crystallinity, and comparable optical properties to the directly synthesized NCs. The relatively slow kinetics and stop-on-demand feature of the transformation reaction allow real-time composition–structure–property investigations of the reaction, thus elucidating a cation-alloyed intermediate-assisted transformation mechanism. Our study presented here demonstrates for the first time that post-synthetic transformation of 0D perovskite NCs can serve as a new route towards the synthesis of high-quality lead-free perovskite NCs, and provides valuable insights into the crystal structures, excitonic properties and their relationships of perovskite NCs.

Lead-free perovskite nanocrystals are synthesized by post-synthetic transformation reactions. The post-synthetic transformations show the structural flexibility of zero-dimensional perovskite nanocrystal materials.     

A Certified Reference Material for HPLC

A column and test samples have been produced as a Certified Reference Material (CRM) for use in HPLC. A round robin certification procedure has demonstrated that the retention and relative retention properties of the column, measured as the values of shape selectivity, hydrophobicity and ion-exchange activity at pH 7.0, under closely specified separation conditions, are reproducible irrespective of the instrument and laboratory. Concurrence with the CRM values can be used to confirm that an HPLC system is compliant with these specifications, in particular the mobile phase composition and column temperature. This will enable different laboratories to determine that they are operating under equivalent separation conditions, which is a necessary requirement for the efficient interlaboratory transferability of methods.