The Design of α/β‐Peptides: Study on Three‐Residue Turn Motifs and the Influence of Achiral Glycine on Helix and Turn

Novel three‐residue helix‐turn secondary structures, nucleated by a helix at the N terminus, were generated in peptides that have ‘β‐Caa‐L ‐Ala‐L ‐Ala,’ ‘β‐Caa‐L ‐Ala‐γ‐Caa,’ and ‘β‐Caa‐L ‐Ala‐δ‐Caa’ (in which β‐Caa is C‐linked carbo‐β‐amino acid, γ‐Caa is C‐linked carbo‐γ‐amino acid, and δ‐Caa is C‐linked carbo‐δ‐amino acid) at the C terminus. These turn structures are stabilized by 12‐, 14‐, and 15‐membered (mr) hydrogen bonding between NH(i)/CO(i+2) (i+2 is the last residue in the peptide) along with a 7‐mr hydrogen bond between CO(i)/NH(i+2). In addition, a series of α/β‐peptides were designed and synthesized with alternating glycine (Gly) and (S)‐β‐Caa to study the influence of an achiral α‐residue on the helix and helix‐turn structures. In contrast to previous results, the three ‘β–α–β’ residues at the C terminus (α‐residue being Gly) are stabilized by only a 13‐mr forward hydrogen bond, which resembles an α‐turn. Extensive NMR spectroscopic and molecular dynamics (MD) studies were performed to support these observations. The influence of chirality and side chain is also discussed.     

Best proximity points: global optimal approximate solutions

Let A and B be non-empty subsets of a metric space. As a non-self mapping \({T:A\longrightarrow B}\) does not necessarily have a fixed point, it is of considerable interest to find an element x in A that is as close to Tx in B as possible. In other words, if the fixed point equation Tx = x has no exact solution, then it is contemplated to find an approximate solution x in A such that the error d(x, Tx) is minimum, where d is the distance function. Indeed, best proximity point theorems investigate the existence of such optimal approximate solutions, called best proximity points, to the fixed point equation Tx = x when there is no exact solution. As the distance between any element x in A and its image Tx in B is at least the distance between the sets A and B, a best proximity pair theorem achieves global minimum of d(x, Tx) by stipulating an approximate solution x of the fixed point equation Tx = x to satisfy the condition that d(x, Tx) = d(A, B). The purpose of this article is to establish best proximity point theorems for contractive non-self mappings, yielding global optimal approximate solutions of certain fixed point equations. Besides establishing the existence of best proximity points, iterative algorithms are also furnished to determine such optimal approximate solutions.     

Phytochemical mediated gold nanoparticles and their PTP 1B inhibitory activity

Current discovery demonstrates the rapid formation of gold nanoparticles with guavanoic acid a phytochemical of Psidium guajava (Pg). The pharmacological capabilities of the phytochemicals present in the leaves of Pg and their ability to generate gold nanoparticles is presented herein. The new genre of green nanoparticles exhibit remarkable Protein Tyrosine Phosphatase 1B (PTP 1B) inhibitory activity and in vitro stability in various physiological medium including saline, histidine, cysteine, bovine serum albumin (BSA), human serum albumin (HSA) and buffers (pH 5, 7 and 9). It is predicted that this new technology will be felt greatly in several routes of pharmaceuticals.     

Transient analysis of a single server queue with catastrophes, failures and repairs

A transient solution is obtained analytically using continued fractions for the system size in an M/M/1 queueing system with catastrophes, server failures and non-zero repair time. The steady state probability of the system size is present. Some key performance measures, namely, throughput, loss probability and response time for the system under consideration are investigated. Further, reliability and availability of the system are analysed. Finally, numerical illustrations are used to discuss the system performance measures.      

Discovery of redox system enabling C–N–C bonds formation: Unprecedented Aza-Cannizzaro reaction

A novel reaction involving in situ redox conversion of glyoxylate esters to glycine is described. Simple starting materials and mild conditions for the synthesis of glycine derivatives probably indicate a pathway towards prebiotic chemistry. This proceeds analogous to Cannizzaro reaction involving ammonia therefore it can be termed as intramolecular Aza-Cannizzaro type reaction. This reaction is examined in detail with an aid of computational analysis to corroborate the proposed mechanism.     

Cytotoxic constituents of Abutilon indicum leaves against U87MG human glioblastoma cells

The study was aimed to identify cytotoxic leads from Abutilon indicum leaves for treating glioblastoma. The petroleum ether extract, methanol extract (AIM), chloroform and ethyl acetate sub-fractions (AIM-C and AIM-E, respectively) prepared from AIM were tested for cytotoxicity on U87MG human glioblastoma cells using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay. These extracts exhibited considerable activity (IC₅₀ values of 42.6–64.5 μg/mL). The most active AIM-C fraction was repeatedly chromatographed to yield four known compounds, methyl trans-p-coumarate (1), methyl caffeate (2), syringic acid (3) and pinellic acid (4). Cell viability assay of 1–4 against U87MG cells indicated 2 as most active (IC₅₀ value of 8.2 μg/mL), whereas the other three compounds were much less active. Interestingly, compounds 1–4 were non-toxic towards normal human cells (HEK-293). The content of 2 in AIM-C was estimated as 3% by HPLC. Hence, presence of some more active substances besides methyl caffeate (2) in AIM-C is anticipated.     

Proteomics Approach to Identify Unique Xylem Sap Proteins in Pierce’s Disease-Tolerant Vitis Species

Pierce’s disease (PD) is a destructive bacterial disease of grapes caused by Xylella fastidiosa which is xylem-confined. The tolerance level to this disease varies among Vitis species. Our research was aimed at identifying unique xylem sap proteins present in PD-tolerant Vitis species. The results showed wide variation in the xylem sap protein composition, where a set of polypeptides with pI between 4.5 and 4.7 and M _r of 31 kDa were present in abundant amount in muscadine (Vitis rotundifolia, PD-tolerant), in reduced levels in Florida hybrid bunch (Vitis spp., PD-tolerant) and absent in bunch grapes (Vitis vinifera, PD-susceptible). Liquid chromatography/mass spectrometry/mass spectrometry analysis of these proteins revealed their similarity to β-1, 3-glucanase, peroxidase, and a subunit of oxygen-evolving enhancer protein 1, which are known to play role in defense and oxygen generation. In addition, the amount of free amino acids and soluble sugars was found to be significantly lower in xylem sap of muscadine genotypes compared to V. vinifera genotypes, indicating that the higher nutritional value of bunch grape sap may be more suitable for Xylella growth. These data suggest that the presence of these unique proteins in xylem sap is vital for PD tolerance in muscadine and Florida hybrid bunch grapes.     

Synthesis of hexahydro-5H-benz[g]imidazo[2,1-a]- isoindole 2 via an intramolecular diels-alder reaction and a novel lawesson's reagent mediated cyclization

The 2-(5,6-dihydroxy-1,2,3,4-tetrahydro-1-naphthyl)imidazoline 1 is a recently reported potent alpha-adrenergic agent [1]. In continuation of our work on the synthesis of potential adrenergic agents we required imidazoisoindole 2 in order to investigate the biological effects of incorporation of additional rigidity into the parent system. This paper describes the synthesis of 2 via an intramolecular Diels-Alder reaction and a novel Lawesson's reagent mediated cyclization.