Spectral studies of complexes of nickel(II) with tetradentate schiff bases having N2O2 donor groups

Complexes of nickel(II) of N,N'-disalicylidene-1,2-phenylenediamine (H2dsp), N,N'-disalicylidene-3,4-diaminotoluene (H2dst), 4-nitro-N,N'-disalicylidene-1,2-phenylenediamine (H2ndsp) and N,N'-disalicylidene ethylenediamine (H2salen) have been prepared and characterised by elemental analysis, electronic, IR, magnetic susceptibility measurement, 1H NMR and thermal studies. TG studies show that the Ni(dsp) and Ni(salen) complex decomposed in one step and Ni(dst) and Ni(ndsp) complex in two steps. Kinetic and thermodynamic parameters were computed from the thermal decomposition data. The activation energy of either one step decomposition or two step decomposition of complexes lies 72-95 kJ mol(-1) range.     

Stable and tunable phosphorescent neutral cyclometalated Au(III) diaryl complexes

A series of novel luminescent cyclometalated Au(III) neutral complexes of the type cis-[(N(∧)C)AuL] [N(∧)C = 2-phenylpyridine (ppy), L = 1,1'-biphenyl (1)] and cis-[(N(∧)C)AuL(2)] [N(∧)C = 2-phenylpyridine (ppy), L = C(6)H(5) (2), C(6)F(5) (3), C(6)H(4)-CF(3)-p (4), 2-C(4)H(3)S (5)]; [N(∧)C = 2-(2-thienyl)pyridine (thpy), L = C(6)H(5) (6), C(6)F(5) (7)]; [N(∧)C = 2-(5-methyl-2-thienyl)pyridine (5 m-thpy), L = C(6)F(5) (8)] were successfully synthesized. The X-ray crystal structures of all compounds except 3 have been determined. These complexes were found to show long-lived emission in solution at room temperature. The emission origins of the complexes have been tentatively assigned to be derived from triplet states predominantly bearing intraligand (IL) character with some perturbation from the metal center. Density functional theory (DFT) calculations were performed to evaluate the stability associated with the complexes and TD-DFT calculations to ascertain the nature of the excited state. Variation of the cyclometalated ligands in the complexes readily leads to the tuning of the nature of the lower energy emissive states.     

Chlorella minutissima—A Promising Fuel Alga for Cultivation in Municipal Wastewaters

It is imperative to slash the cost of algal oil to less than $50 bbl^?1 for successful algal biofuel production. Use of municipal wastewater for algal cultivation could obviate the need for freshwater and the nutrients—N and P. It would also add CO₂ through bacterial activity. Chlorella minutissima Fott et Nova dominated the entire phycoflora year around and through each stage of the wastewater treatment at the oxidation pond system of Wazirabad (Delhi) in India. The ability to grow so profusely in such varied and contrasting situations made this alga unique. Besides pollution tolerance, it grew heterotrophically in dark under acidic conditions and as a mixotroph in presence of light over a range of organic C substrates. It could utilize both ammoniacal and nitrate nitrogen, survived anaerobicity, 5% NaCl and ?10 bar of osmotic stress. C. minutissima grew at pH 4–11 and raised the pH set initially by 1 to 3 units in 7.5 h. It showed gigantism and largely kept afloat in presence of utilizable organic carbon, while flocculated in mineral medium and on aging. The alga also possessed potential for biofuel production. The studied parameters indicate why C. minutissima was a potential biomass builder in municipal sewage and could be used to determine which other alga(e) may serve the purpose.     

Anti-ulcer activity of Smithia conferta in various animal

Smithia conferta Sm. (Leguminasae), is a commonly used plant in Indian traditional medicine. In the current study anti-ulcer activity of its petroleum ether, alcohol and aqueous extracts of leaves were investigated using different animal models. All extracts were also subjected to phytochemical analysis and their toxic potential. Petroleum ether extract was found to contain steroids; alcohol extract revealed the presence of isoflavonoids, alkaloids and carbohydrates; while aqueous extract was found to contain amino acids, carbohydrates and flavonoids. S. conferta aqueous and alcoholic extracts were found to be non-toxic up to 5000 mg/kg dose level while petroleum ether extract was safe only up to a dose of 2000 mg/kg after single dose administration of the extracts.During confirmation of the claimed anti-ulcer activity, treatment with aqueous and alcoholic extracts showed significant reduction in ulcer index, free acidity as well as total acidity in pylorus ligated rats. However, petroleum ether extract showed relatively less profound reduction in all these indices. The anti-ulcer activity observed in aqueous extract treatment group was nearly equivalent to the standard group.     

Single molecule imaging of oxygenation of cobalt octaethylporphyrin at the solution/solid interface: thermodynamics from microscopy

For the first time, the pressure and temperature dependence of a chemical reaction at the solid/solution interface is studied by scanning tunneling microscopy (STM), and thermodynamic data are derived. In particular, the STM is used to study the reversible binding of O(2) with cobalt(II) octaethylporphyrin (CoOEP) supported on highly oriented pyrolytic graphite (HOPG) at the phenyloctane/CoOEP/HOPG interface. The adsorption is shown to follow the Langmuir isotherm with P(1/2)(298K) = 3200 Torr. Over the temperature range of 10-40 °C, it was found that ΔH(P) = -68 ± 10 kJ/mol and ΔS(P) = -297 ± 30 J/(mol K). The enthalpy and entropy changes are slightly larger than expected based on solution-phase reactions, and possible origins of these differences are discussed. The big surprise here is the presence of any O(2) binding at room temperature, since CoOEP is not expected to bind O(2) in fluid solution. The stability of the bound oxygen is attributed to charge donation from the graphite substrate to the cobalt, thereby stabilizing the polarized Co-O(2) bonding. We report the surface unit cell for CoOEP on HOPG in phenyloctane at 25 °C to be A = (1.46 ± 0.1)n nm, B = (1.36 ± 0.1)m nm, and α = 54 ± 3°, where n and m are unknown nonzero non-negative integers.     

Rapid identification of trimethyl and triethyl amines using sulphonic acidic ionic liquids: A time-of-flight secondary ion mass spectrometry study of fragmentation reactions

The time-of-flight secondary ion mass spectrometry (TOF-SIMS) has emerged as a powerful tool for the unswerving detection of biomolecules, in particular, proteins and peptides. To date, there is very little information available on the direct determination of trimethyl/triethyl amines using TOF-SIMS. One major hurdle in this regard is an ultrahigh vacuum system, usually needed in TOF-SIMS, which hampers its usability to trimethyl/triethyl amines owing to their high evaporation rate. We designed an efficient and sensitive protocol for rapid identification and sensitive determination of tertiaryalkyl amines using TOF-SIMS. The amines were derivatized by reaction with 1,4-butane sultone and sulphuric acid sequentially to afford the corresponding sulphonic acidic ionic liquids (ILs). The TOF-SIMS analysis of these task-specific ILs (TSILs) was carried out in both positive and negative polarity. The positive ion mass spectra of TSILs showed sharp fragmented peaks for tertiaryalkyl amines at typical level and up to 10 ppm. The possible mechanism for different fragmentation pathways in positive polarity was discussed.     

Synthesis and studies on metal coordination with a novel carboxyamide ligand

Novel complexes of Co(II), Ni(II), Cu(II) and Pd(II) with the new ligand [N,N'-bis(2-carboxy-1-oxo-phenelenyl)ethylenediamine] (H2L) have been synthesized and characterized on the basis of elemental analyses, magnetic susceptibility, thermal, infrared, electronic, 1H NMR and EPR spectral studies. Infrared and 1H NMR spectra show that H2L acts as a binegative tetradentate ligand. Coordination occurs through deprotonated carboxylate oxygens and nondeprotonated amido nitrogens in all the complexes. Electronic spectral studies and magnetic moment values suggest N2O2 coordination around each metal centre with strong field square planar chromophores. The probable structures of the complexes have been assigned on the basis of spectral studies. The complex formation between M(II) [M(II) = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)] and (L2-) has also been studied potentiometrically in 75% aqueous DMF at 25 degrees C in 0.1 M NaClO4. The stability constants were found to follow the order: Mn(II) < Co(II) < Ni(II) < Cu(II) > Zn(II).     

Cobalt(II) complexes of new biomimetic polydentate amide ligands. A spectroscopic,thermal and potentiometric study

Complexes of Co^II with N,N-bis-(3-carboxy-1-oxopropanyl)-1,2-ethylenediamine(L₁), N,N-bis-(3-carboxy-1-oxopropanyl)-1,2-phenylenediamine(L₂), N,N-bis-(2-carboxy-1-oxophenelenyl)-1,2-phenylenediamine(L₃) and N,N-bis-(3-carboxy-1-oxoprop-2-enyl)-1,2-phenylenediamine(L₄) have been prepared and characterized by elemental analysis, vibrational spectra, magnetic susceptibility measurements, electronic spectra and thermal studies. Stability constants of the complexes have been evaluated potentiometrically. Vibrational spectra indicate coordination of amide and carboxylate oxygens of the ligands along with two water molecules giving a MO₆ weak field octahedral chromophore. Electronic spectra support octahedral geometry around Co^II. The [Co(L₁)-(H₂O)₂] · 2H₂O complex has the maximum activation energy and [Co(L₃)(H₂O)₂] complex has the minimum activation energy. The order of stability constants of the Co^II complexes with various ligands is due to their -donor abilities.     

Metal‐Free Triplet Phosphors with High Emission Efficiency and High Tunability

Design of highly efficient phosphorescent emitters based on metal‐ and heavy atom‐free boron compounds has been demonstrated by taking advantage of the singlet fission process. The combination of a suitable molecular scaffold and appropriate electronic nature of the substituents has been utilized to tailor the phosphorescence emission properties in solution, neat solid, and in doped PMMA thin films.     

Microwave-Assisted Graft Copolymerization of Cellulosic Fibers for Removal of Heavy Metal Ions from Aqueous Solution

Functional materials obtained from cellulosic biofibers have gained attention due to the growing demand for them in the field of wastewater remediation. In view of the technological significance of functionalized cellulosic biofibers in wastewater treatment, the present study is a green approach to functionalized cellulosic fibers through graft copolymerization under microwave irradiation. The grafted cellulosic polymers were subsequently subjected to heavy metal ion adsorption studies in order to assess their application in wastewater remediation. The effects of pH, contact time, temperature, and metal ion concentration were studied in batchwise adsorption experiments. The Langmuir, Freundlich, and Tempkin models were used to show the adsorption isotherms. The maximum monolayer capacities, q _m. calculated using the Langmuir isotherm for Zn²⁺, Cd²⁺, and Pb²⁺ were found to be 37.79, 69.68, and 96.81 mg/g respectively. The thermodynamic parameter ΔH° and ΔG° values for metal ion adsorption on functionalized cellulosic fibers showed that adsorption process was spontaneous as well as exothermic in nature.