Critical behavior of the aqueous electrolytic system 3-methylpyridine+D2O+NaBr

The system 3-methylpyridine(3MP) + water(H2O)+NaBr has been the subject of an intense scientific debate since the work of Jacob et al. [Phys. Rev. E. 58, 2188 (1988)] and Anisimov et al. [Phys. Rev. Lett. 85, 2336 (2000)]. The crossover critical behavior of this system seemed to show remarkable sensitivity to the weight fraction (X) of the ionic impurity NaBr. In the range X< or =0.10 the system displayed Ising behavior and a pronounced crossover to mean-field behavior in the range 0.10< or =X< or =0.16. A complete mean-field behavior was observed at X=0.17, a result that was later attributed to the existence of long-living nonequilibrium states in this system [Kostko et al., Phys. Rev. E. 70, 026118 (2004)]. In this paper, we report the near-critical behavior of osmotic susceptibility in the isotopically related ternary system, 3MP+heavy water(D2O)+NaBr. Detailed light-scattering experiments performed at exactly the same NaBr concentrations as investigated by Jacob et al. reveal that the system 3MP + D2O + NaBr shows a simple Ising-type critical behavior with gamma approximately 1.24 and nu approximately 0.63 over the entire NaBr concentration range 0< or =X< or =0.1900. The crossover behavior is predominantly nonmonotonic and is completed well outside the critical domain. An analysis in terms of the effective susceptibility exponent (gammaeff) reveals that the crossover behavior is nonmonotonic for 0< or =X< or =0.1793 and tends to become monotonic for X>0.1793. The correlation length amplitude xio, has a value of approximately 2 A for 0.0250< or =X< or =0.1900, whereas for X=0, xio approximately 3.179 A. Since isotopic H-->D substitution is not expected to change the critical behavior of the system, our results support the recent results obtained by Kostko et al. [Phys. Rev. E. 70, 026118 (2004)] that 3MP + H2O + NaBr exhibits universal Ising-type critical behavior typical for other aqueous solutions.     

A computational examination on the structure, spin-state energetics and spectroscopic parameters of high-valent Fe(IV)[double bond, length as m-dash]NTs species

The imidoiron(iv) species are relatively less explored compared to the oxoiron(iv) intermediates. Recently, generation and characterization of a novel imido/oxoiron(iv) species ([(N(4)Py)Fe(IV)[double bond, length as m-dash]X](2+) X = NTs; 1, O; 2) has been reported with an S = 1 ground state. Although the ground state for 1 and 2 are the same, they are reported to be distinctly different in other aspects. Unlike the oxoiron(iv) species, the Fe(iv) and nitrene combination in 1 lead to eight different spin states. Bearing in mind the complexity arising here, we have undertaken a detailed DFT study on this transient intermediate and probed its electronic structure and bonding in comparison to the oxoiron(iv) unit. Our Molecular Orbital, Energy Decomposition Analysis, and Natural Bond Orbital analysis indicates a weaker σ and non-degenerate π* orbitals for 1 in comparison to a stronger σ and degenerate π* orbitals for 2. The implication of these intricate bonding differences in reactivity is discussed along with the computation of absorption and other spectral parameters. Our results broadly support the proposed S = 1 ground state for 1 and provides some useful insight into its electronic structure.     

Shape evolution in odd-A 137 Pm

The odd mass nucleus ¹³⁷Pm has been studied to high spins through the ¹⁰⁹Ag(³²S, 2p2n)¹³⁷Pm reaction at an incident beam energy of 150 MeV. The de-exciting ??-rays were detected using an array of 18 Compton suppressed clover detectors. The level scheme of ¹³⁷Pm has been extended up to $J^\pi = \tfrac{{43}} {2}^ -$ and excitation energy of E _x ? 6 MeV with the observation of 42 new gamma transitions. The linear polarization (IPDCO) measurements for the ??-ray transitions have been done for the first time. The spin and parity assignments for most of the reported levels have been made using these results and the coincidence angular anisotropy (R_DCO) measurements. The nuclear shape evolution is discussed in the light of Total Routhian Surface (TRS) and Cranked Shell Model (CSM) calculations.     

Synthesis,characterization, antifungal,antibacterial and DNA cleavage studies of some heterocyclic Schiff base metal complexes

Co(II), Ni(II), Cu(II) and Zn(II) complexes of the Schiff base derived from indole-3-carboxaldehyde and m-aminobenzoic acid were synthesized and characterized by elemental analysis, molar conductance, IR, UV–Vis, magnetic moment, powder XRD and SEM. The IR results demonstrate the bidentate binding mode of the ligand involving azomethine nitrogen and carboxylato oxygen atoms. The electronic spectral and magnetic moment results indicate that Co(II) and Ni(II) complexes have tetrahedral geometry, while Cu(II) complex is square planar. Powder XRD and SEM indicate the crystalline state and surface morphology studies of the complexes. The antimicrobial activity of the synthesized ligand and its complexes were screened by disc diffusion method. The results show that the metal complexes were found to be more active than the ligand. The nuclease activity of the ligand and its complexes were assayed on CT DNA using gel electrophoresis in the presence of H₂O₂. The Cu(II) complex showed increased nuclease activity in the presence of an oxidant when compared to the ligand and other complexes.     

A New Spray Reagent for Detection and Differentiation of Sulfur Compounds in Plant Extracts

JPC – Journal of Planar Chromatography – Modern TLC -     

Shape changes at high spin in 78Kr

High-spin states in ⁷⁸Kr have been studied via the ⁶³Cu (¹⁹F, 2p2n)⁷⁸Kr reaction at a beam energy of 60 MeV using the Indian National Gamma Array (INGA). In this nucleus, lifetimes have been measured upto the I^π=22⁺ level in the yrast positive-parity band and upto the I^π=15^- level in the negative-parity band using the Doppler Shift Attenuation Method (DSAM). The deduced transition quadrupole moments Q_t's are found to decrease with rotational frequency for both the bands.     

A Validated Chiral HPLC Method for the Determination of Enantiomeric Purity of R-β-amino-β-(4-methoxyphenyl) Propionic Acid

A normal phase chiral LC method for chiral purity evaluation of β-amino-β-(4-methoxyphenyl) propionic acid was developed on donor–acceptor (pirkle) column. The chiral stationary phase used was a 250 × 4.6 mm (R, R) Whelk-01 with 5 μm particle size, which was accompanied with a 1 cm long guard column. The “hybrid” pi-electron donor–acceptor based stationary phase (R, R) Whelk-01 was found to be enantiomeric selective for (R) and (S) enantiomers of β-amino-β-(4-methoxyphenyl) propionic acid with a resolution >2.5. The concentration of 2-propanol and TFA in the mobile phase plays an important role on the chrmatographic efficiency and resolution between the enantiomers. The limit of detection and limit of quantification of (S) enantiomer was 0.3 and 1.0 μg mL^-1 for 20 μL injection volume. The percentage RSD of the peak area of six replicate injections of (S) enantiomer at LOQ concentration was 4.5. The percentage recovery of (S) enantiomer from (R) enantiomer samples ranged from 92 to 100. The test solution was observed to be stable up to 24 h after the preparation. The developed method was also checked by different analysts and on different lots of columns, reagents and it was proved to be rugged. The developed normal phase chiral LC method can be used for the determination of the enantiomeric purity of R-β-amino-β-(4-methoxyphenyl) propionic acid.     

A facile and efficient stereoselective synthesis of highly functionalised trisubstituted alkene derivatives of ferrocenealdehyde

The reaction of the Baylis–Hillman adduct 2 of ferrocenealdehyde with various oxygen and carbon nucleophiles in the presence of montmorillonite K10 clay catalyst furnished highly functionalised trisubstituted alkene derivatives of ferrocenealdehyde in excellent yield. Synthetic use of one of products 7 has been demonstrated with the synthesis of a 1,3-diyne ether derivative of ferrocene 16 via an Eglinton coupling reaction.     

Versatile soluble oligomeric styrene supports for peptide synthesis

Soluble oligomeric styrene supports are reported here with high loading capacities of 1.5–1.6 mmol/g similar to resins used in solid phase peptide synthesis. Oligoether and alkyl chains are incorporated into the scaffold to improve the support solubility and act as spacers between the attachment sites. Amino acids have been attached to the support in 59–85% yields and 0.87–1.3 mmol/g loading. The supports have been used to synthesize tri‐ to hexapeptides in 38–64% yields using only 2 equivalents of coupling reagents, which is much lower than the amount of reagents typically used in solid phase synthesis. A modular synthetic approach is used to obtain the supports so that any efficient styrene‐based attachment site can be readily incorporated into our soluble support scaffold. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2501–2509     

Calcium Borohydride

Calcium borohydride reduces both aliphatic and aromatic esters to alcohols completely in the presence of alkene catalysts. The intermediate borates formed during the reduction of aromatic esters are converted to aldehydes with aqueous NaOC1 in good yields.