Antitrypanasomal activity of novel benzaldehyde-thiosemicarbazone derivatives from kaurenoic acid

A series of new thiosemicarbazones derived from natural diterpene kaurenoic acid were synthesized and tested against the epimastigote forms of Trypanosoma cruzi to evaluate their antitrypanosomal potential. Seven of the synthesized thiosemicarbazones were more active than kaurenoic acid with IC?? values between 2-24.0 mM. The o-nitro-benzaldehyde-thiosemicarbazone derivative was the most active compound with IC?? of 2.0 mM. The results show that the structural modifications accomplished enhanced the antitrypanosomal activity of these compounds. Besides, the thiocyanate, thiosemicarbazide and the p- methyl, p-methoxy, p-dimethylamine, m-nitro and o-chlorobenzaldehyde-thiosemicarbazone derivatives displayed lower toxicity for LLMCK? cells than kaurenoic acid, exhibing an IC?? of 59.5 mM.     

A new concise strategy for synthesis of dibenzo[b,f]thiepins and related fused symmetrical thiepin derivatives

A new strategy for preparation of dibenzo[b,f]thiepins and related fused systems in good overall yields is described, featuring ortho-metalation of aromatic or heterocyclic aldehyde acetals followed by treatment with bis(phenylsulfonyl) sulfide for construction of the required bis(aryl)- or bis(heteroaryl) sulfide precursors, which were thereafter subjected to deacetalization, and finally McMurry coupling as the ring-forming step.     

Resveratrol-derived stilbenoids and biological activity evaluation of seed extracts of Cenchrus echinatus L

A phytochemical study of the ethyl acetate fractions from the partition of seeds and roots methanol extracts of Cenchrus echinatus L. led to the isolation of three resveratrol-derived stilbenoids: pallidol (1), carasiphenol C (2) and nepalensinol B (3). The results of a topic anti-inflammatory evaluation, DPPH assay and antiproliferative activity against adenocarcinoma cells (Caco 2) are described.     

Homogeneous liquid-liquid microextraction via flotation assistance coupled with gas chromatography-mass spectrometry for determination of myclobutanil in cucumber,tomato, grape,and strawberry using genetic algorithm

Facile and potent homogeneous liquid–liquid microextraction via flotation assistance method (HLLME-FA) combined with gas chromatography-mass spectrometry was proposed for determination of trace amounts of myclobutanil in fruit and vegetable samples. The paramount parameters, such as extraction and homogeneous solvent types and volumes, ionic strength and extraction time were studied. Under optimum conditions, the detection limit of 0.005 ng g^?1, the linear range of 0.05–100 ng g^?1, and the precision of 3.8% were acquired. A three-layer arti?cial neural network (ANN) model was used with 10 neurons and tan-sigmoid function at hidden layer and a linear transfer function at output layer were developed to predict the process. The results indicated that the proposed ANN model could perfectly predict the process with the mean square error of 0.89%. Then genetic algorithm was utilised to optimise the parameters. The proposed procedure showed satisfactory results for analysis of cucumber, tomato, grape, and strawberry.     

Establishment of a quality system at the Nuclear Analytical Laboratories of the Atomic Energy Authority, Sri Lanka

A quality system according to the requirements of ISO/IEC guidelines has been introduced at the Nuclear Analytical Laboratories of the Atomic Energy Authority, which has received appreciation from International Atomic Energy Agency (IAEA) inspection evaluation reports (RAS/2/010) showing a positive indication to accreditation. The quality system has achieved the “analytical quality” through technical competence by non-conformance management. The experience in the progression towards achieving a quality system is described with examples from zero level to a positive index. This nuclear analytical service laboratory shows long-term stability of performance and enhances its credibility to customers, through the quality system.     

Deciphering the Electronic Transitions of Thiophene-Based Donor-Acceptor-Donor Pentameric Ligands Utilized for Multimodal Fluorescence Microscopy of Protein Aggregates

Anionic pentameric thiophene acetates can be used for fluorescence detection and diagnosis of protein amyloid aggregates. Replacing the central thiophene unit by benzothiadiazole (BTD) or quinoxaline (QX) leads to large emission shifts and basic spectral features have been reported [Chem. Eur. J. 2015 , 21, 15133-13137]. Here we present new detailed experimental results of solvent effects, time-resolved fluorescence and examples employing multi-photon microscopy and lifetime imaging. Quantum chemical response calculations elucidate how the introduction of the BTD/QX groups changes the electronic states and emissions. The dramatic red-shift follows an increased conjugation and quinoid character of the π-electrons of the thiophene backbone. An efficient charge transfer in the excited states S₁ and S₂ compared to the all-thiophene analogue makes these more sensitive to the polarity and quenching by the solvent. Taken together, the results guide in the interpretation of images of stained Alzheimer disease brain sections employing advanced fluorescence microscopy and lifetime imaging, and can aid in optimizing future fluorescent ligand development.     

Distinct Spacing Between Anionic Groups: An Essential Chemical Determinant for Achieving Thiophene‐Based Ligands to Distinguish β‐Amyloid or Tau Polymorphic Aggregates

The accumulation of protein aggregates is associated with many devastating neurodegenerative diseases and the existence of distinct aggregated morphotypes has been suggested to explain the heterogeneous phenotype reported for these diseases. Thus, the development of molecular probes able to distinguish such morphotypes is essential. We report an anionic tetrameric oligothiophene compound that can be utilized for spectral assignment of different morphotypes of β‐amyloid or tau aggregates present in transgenic mice at distinct ages. The ability of the ligand to spectrally distinguish between the aggregated morphotypes was reduced when the spacing between the anionic substituents along the conjugated thiophene backbone was altered, which verified that specific molecular interactions between the ligand and the protein aggregate are necessary to detect aggregate polymorphism. Our findings provide the structural and functional basis for the development of new fluorescent ligands that can distinguish between different morphotypes of protein aggregates.     

Theoretical study on the electronic,structural, properties and reactivity of a series of mono-, di-, tri- and tetrachlorothiophenes as well as corresponding radical cation forms as monomers for conducting polymers

In this paper, electrical and structural properties of mono-, di-, tri- and tetrachlorothiophenes and their radical cations have been studied using the density functional theory and B3LYP method with 6-311++G** basis set. The effects of the number and position of the substituent of chlorine atoms on the properties of the thiophene ring for all chlorothiophenes and their radical cations have been studied. Vibrational frequencies, nuclear chemical shielding constants, spin-density distribution, size and direction of dipole moment vector, ionization potential, electric polarizabilities and NICS values of these compounds have been calculated as well. The analysis of these data showed that double bonds in 3-chlorothiophene are more delocalized and it is the best possible candidate monomer among all chlorothiophenes for the synthesis of corresponding conducting polymers with modified characteristics.     

New syntheses of unsymmetrical thiepins and their selenium analogues

New routes toward fused thiepins and their selenium analogues are described, wherein initial cleavage of suitable diaryl disulfides or selenides bearing masked aldehyde functionalities with an N-protected and metalated indole-3-carbaldehyde acetal or a lithiated 2-bromobenzaldehyde acetal derivative gave a set of unsymmetrical diacetals. Subsequent deacetalization, followed by McMurry coupling, afforded the target unsymmetrical thiepins and selenepins.