Behavior of acetyl modified amino acids in reverse micelles: a non-invasive and physiochemical approach

The well-characterized, monodisperse nature of reverse micelles formed by sodium bis-(2-ethylhexyl)sulfosuccinate/water/isooctane and their usefulness in assimilating compounds of varied interests have been exploited to investigate the effect of acetyl modified amino acids (MAA) viz., N-acetyl-L-glycine (NAG), N-acetyl-L-aspartic acid (NAA) and N-acetyl-L-cysteine (NAC), on the water pool and physiochemical properties. Non-invasive techniques such as FTIR and UV-vis absorption spectroscopy have been employed to analyze the interactions of MAA with core water and the AOT headgroup. The micropolarities on both sides of AOT interface have further been investigated by UV-vis absorption probes, methyl orange (MO) and methylene blue (MB). The dynamics of water and temperature induced percolation process have also been studied. The MAA molecules have been found to assist the process with the increase in water content where as a contrary behavior has been observed with the increase in temperature. Conductivity results have been further rationalized in terms of scaling equations, which delineate the dynamic nature of the percolation process. The results have also been analyzed in the light of activation energy of the percolation process and thermodynamics of droplet clustering.     

A new rapid multicomponent domino reaction for the formation of functionalized benzo[h]pyrazolo[3,4-b]quinolines

A new multicomponent domino reaction for rapid and regioselective synthesis of highly functionalized benzo[h]pyrazolo[3,4-b]quinolines has been established. The reaction can be conducted by using readily available and inexpensive substrates under microwave irradiation within short periods of 10-26 min. Good to excellent chemical yields (61-91%) and complete regioselectivity have been achieved for 22 examples. Tedious work-up procedure can be avoided due to the direct precipitation of products from the reaction solution. The resulting benzoquinolines have been readily converted into quinoxaline-fused benzo[h]isoxazolo[5,4-b]quinoline analogues by treating with benzene-1,2-diamine under microwave irradiation. The structural assignment has been ambiguously confirmed by X-ray analysis. A new mechanism has been proposed for this new multicomponent domino process.     

1,8‐Naphthalimide: A Potent DNA Intercalator and Target for Cancer Therapy

The poor pharmacokinetics, side effects and particularly the rapid emergence of drug resistance compromise the efficiency of clinically used anticancer drugs. Therefore, the discovery of novel and effective drugs is still an extremely primary mission. Naphthalimide family is one of the highly active anticancer drug based upon effective intercalator with DNA. In this article, we review the discovery and development of 1,8‐naphthalimide moiety, and, especially, pay much attention to the structural modifications and structure activity relationships. The review demonstrates how modulation of the moiety affecting naphthalimide compound for DNA binding that is achieved to afford a profile of antitumor activity. The DNA binding of imide and ring substitution at naphthalimide, bisnaphthalimide, naphthalimide‐metal complexes is achieved by molecular recognition through intercalation mode. Thus, this synthetic/natural small molecule can act as a drug when activation or inhibition of DNA function, is required to cure or control the cancer disease. The present study is a review of the advances in 1,8‐naphthalimide‐related research, with a focus on how such derivatives are intercalated into DNA for their anticancer activities.     

alpha-thiocyanation of carbonyl and beta-dicarbonyl compounds using (dichloroiodo)benzene-lead(II) thiocyanate

The combination reagent (dichloroiodo)benzene and lead(II) thiocyanate in dichloromethane effects oxidation of various enol silyl ethers, ketene silyl acetals, and beta-dicarbonyl compounds, thereby providing an efficient and convenient method for alpha-thiocyanation of carbonyl and beta-dicarbonyl compounds.     

Volumetric Investigations on Molecular Interactions of Glycine/<Emphasis Type="SmallCaps">l</Emphasis>-alanine in Aqueous Citric Acid Solutions at Different Temperatures

Apparent molar volumes \((\phi_{V})\) of glycine/l-alanine in water and in aqueous citric acid (CA) solutions of varying concentrations, i.e. (0.05, 0.10, 0.20, 0.30, 0.40 and 0.50) mol·kg^?1 were determined from density measurements at temperatures T?=?(288.15, 298.15, 308.15, 310.15 and 318.15) K and at atmospheric pressure. Limiting partial molar volumes \((\phi_V^{\text{o}})\) and their corresponding partial molar volumes of transfer \((\Delta_{\text{tr}} \phi_{V} )\) have been calculated from the \(\phi_{V}\) data. The negative \(\Delta_{\text{tr}} \phi_{V}\) values obtained for glycine/l-alanine from water to aqueous CA solutions indicate the dominance of hydrophilic–hydrophobic/hydrophobic–hydrophilic and hydrophobic–hydrophobic interactions over ion/hydrophilic–dipolar interactions. Further, pair and triplet interaction coefficients, i.e. \((V_{\text{AB}} )\;{\text{and}}\; (V_{\text{ABB}} )\) along with hydration number \((n_{\text{H}} )\) have also been calculated. The effect of temperature on the volumetric properties of glycine/l-alanine in water and in aqueous CA solutions has been determined from the limiting partial molar expansibilities \((\partial \phi_{V}^{\text{o}} /\partial T)_{p}\) and their second-order derivative \((\partial^{2} \phi_{V}^{\text{o}} /\partial T^{2} )_{{P}}\). The apparent specific volumes \((\nu_{\phi} )\) for glycine and l-alanine tend to approach sweet taste behavior both in the presence of water and in aqueous CA solutions. The \(\nu_{\phi}\) values for glycine/l-alanine increase with increase in concentration of CA at all temperatures studied. This reveals that CA helps in enhancing the sweet taste behavior of glycine/l-alanine which also supports the dominance of hydrophobic–hydrophobic interactions.     

Suberitane sesterterpenoids from the Antarctic sponge Phorbas areolatus (Thiele, 1905)

Following ecological and chemical screenings, the Antarctic sponge Phorbas areolatus was chemically investigated for the first time. Three new suberitane derivatives named isosuberitenone B, 19-episuberitenone B, and isoxaspirosuberitenone were identified together with the known compounds suberitenones A and B, and oxaspirosuberitenone after a thorough inspection of their NMR data. These compounds were found to exhibit moderate cytotoxic activity and their presence in this sponge rules out their use as a chemotaxonomic marker for Suberites sponges.     

A self-assembled tetrapeptide that acts as a “turn-on” fluorescent sensor for Hg2+ ion

The tetrapeptide (Bz-$\mathrm{\Delta }$Phe(p-NPh₂)-l-DOPA(protected)-l-Phe-l-Phe-OMe was designed to incorporate seven phenyl rings so that it’s conformation, self-assembly and application in Hg²⁺ ions sensing could be studied. Peptide molecules adopted an overlapping β-turn of type III/III conformation in crystals. The peptide showed a highly selective turn-on response towards mercuric ion over other metal ions with a 10-fold enhancement in fluorescence intensity. This intensity change coupled with the selectivity of the peptide towards mercury allowed us to demonstrate simple colorimetric dip sensing of Hg²⁺ ions. The technique provides a highly selective and effective way to detect Hg²⁺ ions. The peptide also self-assembled into nanospheres with diameter ranges from 100 to 500?nm. Mercuric ion coordination enabled these peptide nanospheres to aggregate into well-defined nanoparticles. The enhanced fluorescence upon Hg²⁺ addition demonstrates that peptide scaffolds can be exploited in the development of different selective sensors.     

Mn/Cu catalyzed addition of arylboronic acid to nitriles: Direct synthesis of arylketones

A direct and efficient synthesis of arylketones via arylboronic acid addition to nitriles in presence of inexpensive Mn/Cu catalytic system is reported. The use of non-precious Mn and Cu salts has been found to be highly advantageous both in terms of accessibility as well as cost effectiveness. A series of arylboronic acids as well as nitriles were used to synthesize a variety of symmetrical and unsymmetrical arylketones. Based on the literature studies, the reaction mechanism is anticipated to go through an aryl radical intermediate which reacted with the copper activated nitrile to give the desired arylketones after the hydrolysis of the imine intermediate.     

Metal and Non-metal Based Catalysts for Oxidation of Organic Compounds

The oxidation of organic compounds is of extreme importance in synthetic chemistry. The catalysts provide high selectivity towards the oxidation products employing with the oxidants. This review is not intended to give a complete survey of all oxidation catalysis reactions by different catalysts but rather to give a summary of some important catalytic oxidation reactions by different metal and non-metal based catalysts.     

Quantum chemical investigation on the influence of amino substitution on proton affinity of oxazolidin-2-one

The scenarios of preferred protonation sites and the absolute gas-phase proton affinities of C5- and N4-amino derivatives of oxazolidinone (OXA) molecules possessing two oxygen and two nitrogen atoms, are studied to investigate the effect of substitution of amino group on geometry, electronic structure, and proton affinities of these molecules. The natural bond orbital analysis is invoked to obtain the second-order delocalization energies, occupations of lone pairs, charge distribution, and bond orders to rationalize the obtained results. Our findings reveal a strong nucleophilicity of O1 site in C5-amino and N4-amino-substituted OXA isomers just as in un-substituted OXA. The substituent nitrogen in N4-amino-substituted OXA has comparable electrophilicity to O1 site while lesser than acyl oxygen and higher than nitrogen of OXA ring in C5-amino-substituted OXA. The PA values of C5- and N4-amino-substituted OXA isomers span in the range 172.06–205.77 kcal mol^?1 (at CBS-Q). The PA values for the potential sites increase in the range 1.96–27.08 kcal mol^?1 as a result of the amino substitution at C5 and N4 in orientation (b) while exceptionally they decrease by 0.57–2.95 kcal mol^?1 as a result of the amino substitution at N4 in orientation (a). The results for the order of PA values of potential sites have been supported by molecular electrostatic potential maps. Our findings indicate that the factors such as geometrical rearrangements, variations in atomic charge densities and electron delocalization, effect of substituent, intramolecular hydrogen bonding, and electronic changes direct the relative stabilities and proton affinities of N, C5-substituted amino OXA isomers.