α,β-Unsaturated nitroso system—I : The generation and transformations of ω-nitroso camphene

MO calculations predict a pronounced 1,4-dipolar character for the α,β-unsaturated nitroso synthon, much above that for traditional systems like the α,β-unsaturated Nitro and α,β-unsaturated carbonyl. The work on ω-nitroso camphene-generated from interalia ω-Nitrocamphene 3 is in agreement with the expectations. Thus, the 3 → tricyclene aldehyde 4 change is rationalized on the basis of a σ shift and the 5 → 20 and 6 → 21 changes highlight the overwhelming influence of the α,β-unsaturated nitroso synthon over even the enol ether and enamine functions present in 5 and 6. Amongst other noteworthy features are the deep seated 3 → 8 rearrangement and the preparation and transformation of the extraordinarily stable and the first reported bridgehead nitrile oxide 14.     

Application of a Multilayer Perceptron Artificial Neural Network for the Prediction and Optimization of the Andrographolide Content in Andrographis paniculata

Andrographolide, the principal secondary metabolite of Andrographis paniculata, displays a wide spectrum of medicinal activities. The content of andrographolide varies significantly in the species collected from different geographical regions. Therefore, this study aims at investigating the role of different abiotic factors and selecting suitable sites for the cultivation of A. paniculata with high andrographolide content using a multilayer perceptron artificial neural network (MLP-ANN) approach. A total of 150 accessions of A. paniculata collected from different regions of Odisha and West Bengal in eastern India showed a variation in andrographolide content in the range of 0.28–5.45% on a dry weight basis. The MLP-ANN was trained using climatic factors and soil nutrients as the input layer and the andrographolide content as the output layer. The best topological ANN architecture, consisting of 14 input neurons, 12 hidden neurons, and 1 output neuron, could predict the andrographolide content with 90% accuracy. The developed ANN model showed good predictive performance with a correlation coefficient (R²) of 0.9716 and a root-mean-square error (RMSE) of 0.18. The global sensitivity analysis revealed nitrogen followed by phosphorus and potassium as the predominant input variables influencing the andrographolide content. The andrographolide content could be increased from 3.38% to 4.90% by optimizing these sensitive factors. The result showed that the ANN approach is reliable for the prediction of suitable sites for the optimum andrographolide yield in A. paniculata.     

Magnetic transitions and structure of a NiMnGa ferromagnetic shape memory alloy prepared by melt spinning technique

A ferromagnetic shape memory alloy with nomial composition Ni_52.5Mn_24.5Ga₂₃ (at%) was developed by a melt spinning technique. The as-spun ribbon showed dominant L2₁ austenitic (cubic) structure with a splitting of the primary peak in the X-ray diffractogram indicating the existence of a martensitic feature. The quenched-in martensitic plates were revealed in transmission electron microscopy. An increase of magnetization at low temperature indicated a martensite to austenite transformation and its reverse with a drop in magnetization during the cooling cycle. Higher magnetic fields propel martensite–austenite transformation spontaneously.     

Antimicrobial secondary metabolites of an endolichenic Aspergillus niger isolated from lichen thallus of Parmotrema ravum

Abstract

A new 6-benzyl-γ-pyrone (1), named aspergyllone was isolated from the culture filtrates of an endolichenic fungus Aspergillus niger Tiegh, obtained from lichen thallus Parmotrema ravum (Krog & Swinscow) Serus, collected in India. 1 was isolated for the first time from an endolichenic fungus together with six other known metabolites identified as aurasperones A (2) and D (3), asperpyrone A (4), fonsecinone A (5), carbonarone A (6) and pyrophen (7). The compounds were tested against a panel of human, plant, food borne and fish pathogens. Aspergyllone showed strong selective antifungal activity against Candida parapsilosis (Ashford) Langeron & Talice, with an IC₅₀ of 52?µg/mL. Aurasperone A and pyrophen showed moderate to strong antimicrobial activity inhibiting seven different test pathogens, being pyrophen active with IC₅₀ ranging from 35 to 97?µg/mL.

     

Fourier transform ion cyclotron resonance mass spectrometry in the speciation of high molecular weight sulfur heterocycles in vacuum gas oils of different boiling ranges

The analysis of sulfur aromatics in vacuum gas oils (VGO) distilled from an Iranian light crude oil is discussed. The VGOs were fractionated into three boiling ranges, 390–460, 460–520, and 520–550 °C, and were analyzed using liquid chromatographic separation on a Pd(II)-bonded stationary phase followed by identification with electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). It was possible to detect a large number of thiophenes, including a substantial number of isomers, in the three VGO fractions. Separation on the palladium phase and inclusion of sulfur-selective derivatization makes electrospray ionization of these nonpolar compounds possible. An elemental composition can be assigned to a large number of S₁ compounds without ambiguity in the presence of abundant hydrocarbons. With an increase in boiling temperature, an increase in the size of the aromatic system and the number of side chain carbon atoms was observed. In addition, the masses of higher magnitude shifted toward larger aromatic systems with an increase in boiling range. A comparison of FT-ICR MS and comprehensive gas chromatography is also given. This work is dedicated to Prof. B. Krebs on the occasion of his 70th birthday.     

Anticancer and antimicrobial metallopharmaceutical agents based on palladium, gold, and silver N-heterocyclic carbene complexes

Complete synthetic, structural, and biomedical studies of two Pd complexes as well as Au and Ag complexes of 1-benzyl-3-tert-butylimidazol-2-ylidene are reported. Specifically, trans-[1-benzyl-3-tert-butylimidazol-2-ylidene]Pd(pyridine)Cl2 (1a) was synthesized from the reaction of 1-benzyl-3-tert-butylimidazolium chloride (1) with PdCl2 in the presence of K2CO3 as a base. The other palladium complex, [1-benzyl-3-tert-butylimidazol-2-ylidene]2PdCl2 (1b), and a gold complex, [1-benzyl-3-tert-butylimidazol-2-ylidene]AuCl (1c), were synthesized by following a transmetallation route from the silver complex, [1-benzyl-3-tert-butylimidazol-2-ylidene]AgCl (1d), by treatment with (COD)PdCl2 and (SMe2)AuCl, respectively. The silver complex 1d in turn was synthesized by the reaction of 1 with Ag2O. The molecular structures of 1a-d have been determined by X-ray diffraction studies. Biomedical studies revealed that, while the palladium complexes 1a and 1b displayed potent anticancer activity, the gold (1c) and silver (1d) complexes exhibited significant antimicrobial properties. Specifically, 1b showed strong antiproliferative activity against three types of human tumor cells, namely, cervical cancer (HeLa), breast cancer (MCF-7), and colon adenocarcinoma (HCT 116), in culture. The antiproliferative activity of 1b was found to be considerably stronger than that of cisplatin. The 1b complex inhibited tumor cell proliferation by arresting the cell cycle progression at the G2 phase, preventing the mitotic entry of the cell. We present evidence suggesting that the treated cells underwent programmed cell death through a p53-dependent pathway. Though both the gold (1c) and silver (1d) complexes showed antimicrobial activity toward Bacillus subtilis, 1c was found to be ca. 2 times more potent than 1d.     

Rovibrational energy transfer in ortho-H2+para-H2 collisions

We present the results of a full-dimensional quantum mechanical study of the rovibrational energy transfer in the collision between ortho-H2 and para-H2 in the energy range of 0.1-1.0 eV. The multiconfiguration time-dependent Hartree algorithm has been used to propagate the wave packets on the global potential energy surface by Boothroyd et al. [J. Chem. Phys. 116, 666 (2002)] and on a modification of this surface where the short range anisotropy is reduced. State-to-state attributes such as probabilities or integral cross sections are obtained using the formalism of Tannor and Weeks [J. Chem. Phys. 98, 3884 (1993)] by Fourier transforming the correlation functions. The effect of initial rotation of the diatoms on the inelastic and de-excitation processes is investigated.     

A water-soluble polythiophene-Au nanoparticle composite for pH sensing

In this paper, we report the development of a reversible pH sensor in aqueous medium based on the fluorescence properties of a polythiophene-gold nanoparticle (Au NP) composite. The composite was synthesized in water by simultaneous reduction of HAuCl(4) to Au NPs and polymerization of thiophene in the presence of no additional reagents. It was stable for weeks and had characteristic emissions, which changed in the pH range of 3.0 to 6.0, thus providing a mean for probing the pH of an aqueous solution. Measurement of the pH could be performed over several cycles of titrations, pointing to the robustness of the materials for such sensing applications. The mass spectra of the composite at two extreme pH values were identical, indicating that the primary structure of the polymer was not affected due to changes in pH of the medium. Transmission electron microscopic (TEM) measurements indicated the presence of small sized Au NPs with the polymer in the milieu. The composite could be titrated by acid (or base) and considering the acid-base equilibria at different pHs, we have been able to calculate the pK(eq) of the composite, which was further used in calculating the pH of an aqueous solution from the emission spectrum of the composite. Our approach took advantage of redox chemistry in synthesizing the water-soluble composite and the optical behavior of a conjugated polymer in developing an important pH sensor, which may form the basis of further development of versatile pH or other sensors by suitably modifying the backbone of the monomer.     

Periodicity of Balancing Numbers

The balancing numbers originally introduced by Behera and Panda [2] as solutions of a Diophantine equation on triangular numbers possess many interesting properties. Many of these properties are comparable to certain properties of Fibonacci numbers, while some others are more interesting. Wall [14] studied the periodicity of Fibonacci numbers modulo arbitrary natural numbers. The periodicity of balancing numbers modulo primes and modulo terms of certain sequences exhibits beautiful results, again, some of them are identical with corresponding results of Fibonacci numbers, while some others are more fascinating. An important observation concerning the periodicity of balancing numbers is that, the period of this sequence coincides with the modulus of congruence if the modulus is any power of 2. There are three known primes for which the period of the sequence of balancing numbers modulo each prime is equal to the period modulo its square, while for the Fibonacci sequence, till date no such prime is available.