Synthesis and spectroscopic studies on complexes of N,N'-bis-(2-pyridinecarboxaldimine)-1,8-diaminonaphthalene (L); DNA binding studies on Cu(II) complex

The Schiff base ligand, N,N'-bis-(2-pyridinecarboxaldimine)-1,8-diaminonaphthalene (L), obtained by the condensation of 2-pyridinecarboxaldehyde and 1,8-diaminonaphthalene, has been used to synthesize the mononuclear complexes of the type [MLCl(2)] [M=Co(II), Ni(II), Cu(II) and Zn(II)]. The newly synthesized ligand (L) and its complexes have been characterized on the basis of results of elemental analysis, molar conductance, magnetic susceptibility measurements, Job's method and spectroscopic studies viz., FT-IR, Mass, (1)H and (13)C NMR. The UV-vis and magnetic moment data revealed an octahedral geometry around Co(II), Ni(II) and Cu(II) ions and conductivity data show a non-electrolytic nature of the complexes. Absorption and fluorescence spectroscopic studies support that Cu(II) complex exhibits significant binding to calf thymus DNA.     

Linking solution chemistry to crystal nucleation: the case of tetrolic acid

The application of FTIR spectroscopy to concentrated solutions of tetrolic acid shows, for the first time, a direct relationship between molecular self association in solution and H-bonded motifs in the subsequently crystallised solid phases.     

Determination of arsenite with N-bromosuccinimide using bordeaux red as an indicator

In this paper the use of N-bromosuccinimide as a direct titrant for AS(III) has been described. Bordeaux red was used as an indicator. From 0.6–6.0 mg of AS(III) were analyzed, and the maximum relative standard deviation is 1.35% in case of 0.60 mg. The method is precise, accurate, and rapid.     

New barium,strontium and strontium‐doped barium squarates: synthesis,crystal structures and DNA/BSA binding,antioxidant and in vitro cytotoxicity studies

A new set of differently hydrated barium and strontium squarates, namely poly[[triaqua(μ‐1,2‐dioxocyclobut‐3‐ene‐1,2‐diolato)barium] monohydrate], {[Ba(C₄O₄)(H₂O)₃]·H₂O}_n ( 1 ), poly[[diaqua(μ‐1,2‐dioxocyclobut‐3‐ene‐1,2‐diolato)strontium] monohydrate], {[Sr(C₄O₄)(H₂O)₂]·H₂O}_n ( 2 ), and poly[[triaqua(μ‐1,2‐dioxocyclobut‐3‐ene‐1,2‐diolato)barium/strontium(0.85/0.15)] monohydrate], {[Ba_0.85Sr_0.15(C₄O₄)(H₂O)₃]·H₂O}_n ( 3 ), is reported. The study of their crystal structures indicates that all the complexes crystallize in the triclinic space group P. Complexes 1 and 3 have a rare combination of squarate units coordinated through monodentate O atoms to two different metal atoms and through two bidentate O atoms to three different metal atoms. Furthermore, they have three coordinated water molecules to give a coordination number of nine. The squarate ligands in complex 2 exhibit two different coordination modes: (i) monodentate O atoms coordinated to four different Sr atoms and (ii) two monodentate O atoms coordinated to two different metal atoms with the other two O atoms bidentate to four different Sr atoms. All the compounds decompose to give the respective carbonates when heated to 800 °C, as evidenced by thermogravimetry/differential thermal analysis (TG‐DTA), which are clusters of nanoparticles. Complexes 1 and 3 show additional endothermic peaks at 811 and 820 °C, respectively, indicating the phase transition of BaCO₃ from an orthorhombic (α‐Pmcn) to a trigonal phase (β‐R3m). All three complexes have significant DNA‐binding constants, ranging from 2.45 × 10⁴ to 9.41 × 10⁴ M^?1 against EB‐CT (ethidium bromide–calf thymus) DNA and protein binding constants ranging from 1.1 × 10⁵ to 8.6 × 10⁵ with bovine serum albumin. The in vitro cytotoxicity of the complexes is indicated by the IC₅₀ values, which range from 128.8 to 261.3 µg ml^?1. Complex 3 shows better BSA binding, antioxidant activity against the DPPH radical and cytotoxicity than complexes 1 and 2 .     

Synthesis and spectral studies of a 12-membered tetraimine macrocyclic ligand and its complexes

[2 + 2] Condensation between 3,4-diaminobenzophenone and benzil in a 1:1 molar ratio in methanol at room temperature resulted in the formation of a novel Schiff base tetraimine macrocyclic ligand, (L): 5,6;11,12-dibenzophenone-2,3;8,9-tetraphenyl-1,4,7,10-tetraazacyclo-dodeca-1,3,7,9-tetraene. The macrocyclic complexes of the type, [FeLCl₂]Cl and [MLCl₂] [M = Co(II) and Cu(II)] have been prepared by reacting iron(III) chloride or metal(II) chlorides with the ligand, L in 1:1 molar ratio in methanol. The stoichiometry corresponding to the formation of the ligand framework, L was ascertained on the basis of results of elemental analyses,¹H-NMR and FAB-mass measurements while that of complexes were ascertained by results of elemental analyses and in solution by Job’s method. The mode of bonding and the geometry of the complexes have been confirmed on the basis of i.r., u.v.–vis spectral findings and magnetic susceptibility measurements which revealed an octahedral geometry for all the complexes. The nature of the complexes was confirmed by conductometric studies.     

Conformational control and photoenolization of pyridine-3-carboxaldehydes in the solid state: stabilization of photoenols via hydrogen bonding and electronic control

We have investigated the solid-state photobehavior of a broad set of pyridine-3-carboxaldehydes 1-5. The introduction of a heteroatom into mesitaldehydes as in aldehydes 1 raises the question of conformational preference in the solid state. The preferred conformations have been unequivocally established from X-ray crystal structure analyses of two of the aldehydes, 1c and 2c; it is shown that intramolecular hydrogen bonding could be utilized to achieve conformational control. In contrast to mesitaldehydes, which undergo efficient photocyclization to benzocyclobutenols in the solid state, the heteroatom analogues 1b and 1c exhibit a perceptible color change (from colorless to pale yellow for 1b and yellow-orange for 1c) upon UV irradiation; the color attributed to (E)-enols is persistent for several hours. Continued irradiation leads to an intractable polymeric material. The AM1 calculations, which have been reliably applied to the thermal cyclization of xylylenols to benzocyclobutenols, reveal that the (E)-enols of 1 are more stable than those of the mesitaldehydes relative to their corresponding benzocyclobutenols. The stabilization is interpreted as arising from the possibility of engaging the heteroatom in resonance delocalization. That the contribution from such a role of the nitrogen atom is so pronounced is elegantly demonstrated by forming the fluoroborate salts; 1a-HBF(4) and 1b-HBF(4) readily exhibit highly red-shifted absorption upon exposure to UV radiation as a result of stabilization of the photoenols. Notably, such a remarkable stabilization via electronic control of the photoenols is unprecedented. All of the 2-methoxy- and 2-chloro-substituted aldehydes 2-5 exhibit photochromism. Ab initio calculations show that the methoxy group in aldehydes 2 and 3 stabilizes the (E)-enols via O[bond]H...O hydrogen bonding as compared to those of 1 by 5-6 kcal/mol relative to their corresponding benzocyclobutenols. Thus, the presence of methoxy and halo groups at position 2 serves not only to direct the formyl oxygen toward the methyl group for H-abstraction but also to stabilize the (E)-enols.     

A new biflavonoid from leaves of Garcinia nervosa

The isolation of a new biflavonoid, identified as I-3, II-3, I-5, II-5, I-7, II-7, I-4', II-4'-octahydroxy [I-2', II-2'] biflavone, from the leaves of Garcinia nervosa is reported. The structure was established by chemical and physical means (IR, UV, 1H-NMR, 13C-NMR data).     

Oxidation of acetanilide by MnO 4 − in the presence of HClO4. A kinetic study

The permanganate ion oxidation of acetanilide was studied spectrophotometrically by measuring the changes in absorbance at 525 nm in perchloric acid solutions. At lower [H⁺], the formation of an intermediate was observed whereas at higher [H⁺], the nature of reaction-time curve was sigmoid. The reaction rate increases with [H⁺] and the kinetics reveals complex order dependence in [H⁺]. The kinetic data for the oxidation of acetanilide indicate that the mechanism involves two steps. The order in [acetanilide] was found to be one. Water soluble Mn(IV) has been identified as an intermediate in the reduction of MnO ₄ ⁻ by acetanilide. The hydrogen ions have been found to decrease the stability of the Mn(IV). Externally added Mn(II) (a product of the reaction) has a composite effect (inhibition and catalysis). The addition of F⁻in the form of NaF has no effect on the reaction rate. The Arrhenius equation was valid for the reaction between 40 and 60 °C. The energy of activation, enthalpy and entropy of activation have been evaluated. Mechanisms consistent with the observed kinetics results have been suggested.     

Excellent electromagnetic interference shielding effectiveness of chemically reduced graphitic oxide paper at 101 GHz*

Graphitic oxide (GO) was synthesized by oxidation of graphite powder using Hummer’s method and the formed GO is solution processed into paper-like macroscopic form. Subsequently, chemically reduced graphitic oxide paper (CRGOP) is prepared by hydrazine vapours induced reduction of formed GO precursor based paper. The formation of GO and its successful reduction to RGO phase is confirmed by FTIR, Raman Spectroscopy and X-ray diffraction. It has been observed that due to high electrical conductivity ~200 micron thick CRGOP display excellent EMI shielding performance at very high frequency of 101 GHz frequency with total shielding effectiveness (SE) value of ?35.49 dB (i.e. >99.97% blocking of incident EM radiation) which is much higher compared to pristine GO paper (?1.55 dB) or comparable to expanded graphite (EG) sheet (?35.61 dB). Due to their lightweight nature, these freestanding CRGOPs display average specific SE value of ?221.8 dB cm³/g. Besides, their excellent flexibility and makes them potential candidate for lightweight EMI gasketing material compared to other forms of flexible carbons like EG.