From a biogenetic scenario to a synthesis of the ABC ring of manzamine A

On the basis of a biogenetic proposal for explaining the biogenesis of manzamine A, the cycloaddition of dihydropyridinium salt 26 with diene derivative 5 leads to adducts 27. These adducts, as well as their related and previously described analogues 9, are now shown to be precursors of diene derivatives such as 10, 13, and 28. Treatment of diene 32 with sodium azide resulted in a one-step formation of the tricyclic imino derivative 34. This key intermediate was further transformed into tricyclic derivative 40, which possesses the essential features of the ABC ring of manzamine A.     

The unusual cyclic products from tetra- and penta-peptides of α-methylalanine

Tetra- and pentapeptides of α-methylalanine give with PCl₅, SOCl₂ etc. intermediates which, with or without loss of amino adds, lead to bi- and tricyclic products containing imidazole and piperazine rings through different routes.     

Synthesis and characterization of platinum(II) and (IV) complexes containing hexamethyleneimine ligand: crystal structure of [Pt(hexamethyleneimine)2(cyclobutanedicarboxylato)]·H2O

A series of new platinum(II) and platinum(IV) complexes of the type [Pt^II(HMI)₂X] (where HMI=hexamethyleneimine, X=dichloro, sulfato, 1,1-cyclobutanedicarboxylato [CBDCA], oxalato, methylmalonato, or tatronato) and [Pt^IV(HMI)₂Y₂Cl₂] (where Y=hydroxo, acetato, or chloro) were synthesized and characterized by infrared (IR) spectroscopy, ¹³C and ¹⁹⁵Pt nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. Among the complexes synthesized, [Pt^II(hexamethyleneimine)₂(1,1-cyclobutanedicarboxylato)]·H₂O was examined by single-crystal X-ray diffraction. The slightly distorted square planar coordination environment of the platinum metal includes the amino group of the hexamethyleneimine (HMI) molecule and the oxygen atoms of the carboxylato ligand. The cyclobutanedicarboxylic acid (CBDCA) molecule adopts six-member chelating rings with platinum. Hydrogen bonding plays an important part in holding the crystal lattice together.     

Unsteady incompressible flow of magnetized aluminium oxide and titanium oxide nanoparticles with blood base fluid

In this investigation, a mixed convective nanoparticles fluid flow over an inclined plate is deliberated. The effects of slip boundary wall and magnetic field are also considered. The dimensionless governing system for the considered problem is attained by implementing recent definitions of fractional derivatives (FD). The generalized solution is obtained through the Laplace Transformation Scheme (LTS) for the momentum and thermal expressions. To improve the novelty and to demonstrate some more physical perception of the stated research work, some remarkable special cases of velocity distribution through CF and AB-fractional derivative concept are addressed, whose daily life implication is well known in the existing literature. Moreover, to evaluate the physical interest of the stated problem, the outcomes of the obtained system graphical illustrations are made by utilizing MATHEMATICA. As a result, we concluded that the aluminium oxide $A{l}_2{O}_3$ nanoparticles show more decaying behavior as compared to titanium oxide $Ti{O}_2$ nanoparticles for temperature and velocity profile. Furthermore, both fields i.e., momentum and thermal distributions are increased with the help of rising estimations parameter. Current results report novel applications in enhancement of heat transfer, thermal engineering, chemical processes, engineering and electronics devices, solar systems, extrusion processes, fission reactions etc.     

INVESTIGATION OF THE ALLOMERIZATION REACTION OF CHLOROPHYLL a: USE OF DIODE ARRAY HPLC, MASS SPECTROMETRY AND CHEMOMETRIC FACTOR ANALYSIS FOR THE DETECTION OF EARLY PRODUCTS

Abstract –The products of chlorophyll allomerization in methanol were isolated and analyzed by open column sucrose chromatography, liquid chromatography mass spectrometry (LCMS) and DAD-HPLC (diode-array high-performance liquid chromatography). Four main bands were found with molecular ions of (a) 908, (b) 938, (c) 938 and (d) 938, consistent with the structures (a) 13²-hydroxy-chlorophyll a (II), (b) and (c) Mg(II)-3¹,3²-didehydro-15¹-hydroxy-15¹-methoxy-rhodochlorin-15 acetic acid δ-lactone 15²-methyl 17³-phytyl ester and its epimer (III) and (d) Mg(II)-3¹,3²-didehydro-rhodochlorin-15-glyoxylic acid 13¹,15²-dimethyl 17³-phytyl ester (IV), evidence enhanced by UV/visible spectroscopy, chromatographic coelutions and chemometrics. Chlorophyll a was degraded both in the dark and light, under O₂ and N². DAD-HPLC of the resultant degradation mixtures were analyzed using the chemometric heuristic-evolving latent projection method for resolution. Ultraviolet/visible spectra of II and III are reproducibly extracted from the mixtures after a short degradation time, whereas III and IV are the dominant compounds after longer degradation times. Changes in relative elution order of IV using open column chromatography and reverse-phase HPLC are established. A possible allomerization pathway is proposed.     

Quantitative determination of Malathion in pesticide by modified attenuated total reflectance-Fourier transform infrared spectrometry applying genetic algorithm wavelength selection method

A simple and environment friendly method was developed for determination of Malathion content of analytical and commercial insecticide samples with no special preparation. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectra were characterized and 1000-2000 cm⁻¹ region was selected for quantitative analysis utilizing partial least square (PLS) and two wavelength selection methods: (a) principal component regression (PCR) and (b) genetic algorithm (GA). Relative error of prediction (REP) was calculated in PLS, PCR-PLS and GA-PLS methods and was 3.536, 1.656 and 0.188, respectively. Proposed method is successfully applicable for quantification of Malathion in commercial grade samples and reliable results in comparison with known methods, confirms this idea.     

Synergic effect of triphenylphosphine oxide (TPPO) on the extraction of Hg(II), Se(IV), Co(II) and Mn(II) with fluorinated pyrazolone (HPMTFP)

Extraction of Hg(II), Se(IV), Mn(II) and Co(II) has been carried out with 1-phenyl-3-methyl-4-trifluoroacetyl-2-pyrazolin-5-one (HPMTFP) and triphenylphosphine oxide (TPPO) into chloroform from pH 1–10. Quantitative extraction of Hg(II), Mn(II) and Co(II) at pH 4 with equimolar 0.05M (PMTFP+TPPO) in chloroform was observed. Se(IV) remains unextracted at this pH range. The stoichiometric composition of the extracted complexes M(PMTFP)₂·nH₂O (M=Mn, Hg), M(PMTFP)₂·2TPPO (M=Mn and Co) and Co(PMTFP)₂·TPPO·H₂O at less than 0.1M TPPO has been established. The formation constantsK _m,0 andK _m,n and stability constants _m,n have been computed. The analytical method developed was applied to the IAEA standard reference material (SRM) potato fluor V-4 for the determination of these elements using NAA technique.     

2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol as a reagent for the spectrophotometric determination of La(III), Y(III), and Ce(III)

The complexes of the reagent 5-Br-PADAP with the metal ions La(III), Ce(III), and Y(III) have been studied.The composition and stability of these complexes have been determined. A sensitive spectrophotometric procedure for the determination of the metal ions La(III), Ce(III), and Y(III) has been proposed. The limitations of this procedure and the effect of other ions have been studied.     

The reaction of (N-isocyanimino)triphenylphosphorane with benzoic acid derivatives: a novel synthesis of 2-aryl-1,3,4-oxadiazole derivatives

The reactions of benzoic acid derivatives with (N-isocyanimino)triphenylphosphorane proceed smoothly at room temperature to afford 2-aryl-1,3,4-oxadiazoles in high yields.     

Enantioselective total syntheses of manzamine a and related alkaloids

As a prelude to undertaking the total syntheses of the complex manzamine alkaloids, a series of model studies were conducted to establish the scope and limitations of intramolecular [4 + 2] cycloadditions of N-acylated vinylogous ureas with the trienic substrates 17a,b, 28a,b, and 34. These experiments clearly demonstrated that the geometry of the internal double bond and the presence of an electron-withdrawing group on the diene moiety were essential for the facile and stereoselective formation of the desired cycloadducts. The enantioselective syntheses of the manzamine alkaloids ircinol A (75), ircinal A (5), and manzamine A (1) were then completed by employing a convergent strategy that featured a novel domino Stille/Diels-Alder reaction to construct the tricyclic ABC ring core embodied in these alkaloids. Thus, the readily accessible chiral dihydropyrrole 58 was first converted in a single chemical operation into the key tricyclic intermediate 60. Two ring-closing metathesis reactions were then used to form the 13- and 8-membered rings leading to Z-72 and 74, the latter of which was quickly elaborated into ircinal A (5) via ircinol A (75). The synthetic 5 thus obtained was converted into manzamine A (1) following literature precedent. This concise synthesis of ircinal A required a total of 24 operations from commercially available starting materials with the longest linear sequence being 21 steps.