Noncovalent assembly of ferrocene on modified gold surfaces mediated by uracil–adenine base pairs

Redox-active ferrocene was assembled on gold surfaces through the hydrogen bonding interactions between adenine-substituted ferrocene and a uracil-terminated organothiol monolayer. The surface coverage of ferrocene Γ could be varied from ca. 4 × 10^? 11 to 2.0 × 10^? 10 mol cm^? 2 by diluting the thiol-modified uracil derivative with inert 1-octanethiol. A decrease in the apparent electron transfer rate constant for ferrocene, k_app, from ca. 50 to 10 s^? 1 was observed upon increasing Γ.     

Theoretical studies of decomposition kinetics of CF3CCl2O radical

The unimolecular decomposition reaction of CF₃CCl₂O radical has been investigated using theoretical methods. Two most important channels of decomposition occurring via C–C bond scission and Cl elimination have been considered during the present investigation. Ab initio quantum mechanical calculations are performed to get optimized structure and vibrational frequencies at DFT and MP2 levels of theory. Energetics are further refined by the application of a modified Gaussian-2 method, G2M(CC,MP2). The thermal rate constants for the decomposition reactions involved are evaluated using Canonical Transition State Theory (CTST) utilizing the ab initio data. Rate constants for C–C bond scission and Cl elimination are found to be 6.7 × 10⁶ and 1.1 × 10⁸ s^?1, respectively, at 298 K and 1 atm pressure with an energy barrier of 8.6 and 6.5 kcal/mol, respectively. These values suggest that Cl elimination is the dominant process during the decomposition of the CF₃CCl₂O radical. Transition states are searched on the potential energy surface of the decomposition reactions involved and are characterized by the existence of only one imaginary frequency (NIMAG = 1) during frequency calculation. The existence of transition states on the corresponding potential energy surface is further ascertained by performing intrinsic reaction coordinate (IRC) calculation.     

Properties of Ionic Liquid Confined in Porous Silica Matrix

Porous silica matrices of different pore sizes with confined ionic liquid (1‐butyl‐3‐methylimidazolium hexafluorophosphate) [BMIM] [PF₆] were prepared by sol‐gel technique using a tetraethyl orthosilicate (TEOS) precursor with an aim to study the changes in physico‐chemical properties of ionic liquid on confinement. It is found that on confinement 1) melting point decreases, 2) fluorescence spectra shows a red shift and 3) the vibrational bands are affected particularly those of imadazolium ring, which interacts more with the walls of the silica matrix. Preliminary theoretical calculations suggest that SiO₂ matrix interact more with the heterocyclic group of [BMIM] cation than the tail alkyl chain end group resulting in significant changes in the aromatic vibrations.     

Sonochemical synthesis of Ce(1-x)Fe(x)O(2-δ) (0 ≤ x ≤ 0.45) and Ce(0.65)Fe(0.33)Pd(0.02)O(2-δ) nanocrystallites: oxygen storage material, CO oxidation and water gas shift catalyst

Nanocrystalline Ce(1-x)Fe(x)O(2-δ) (0 ≤ x ≤ 0.45) and Ce(0.65)Fe(0.33)Pd(0.02)O(2-δ) of ~4 nm sizes were synthesized by a sonochemical method using diethyletriamine (DETA) as a complexing agent. Compounds were characterized by powder X-ray diffraction (XRD), X-ray photo-electron spectroscopy (XPS) and transmission electron microscopy (TEM). Ce(1-x)Fe(x)O(2-δ) (0 ≤ x ≤ 0.45) and Ce(0.65)Fe(0.33)Pd(0.02)O(2-δ) crystallize in fluorite structure where Fe is in +3, Ce is in +4 and Pd is in +2 oxidation state. Due to substitution of smaller Fe(3+) ion in CeO(2), lattice oxygen is activated and 33% Fe substituted CeO(2)i.e. Ce(0.67)Fe(0.33)O(1.835) reversibly releases 0.31[O] up to 600 °C which is higher or comparable to the oxygen storage capacity of CeO(2)-ZrO(2) based solid solutions (Catal. Today 2002, 74, 225-234). Due to interaction of redox potentials of Pd(2+/0)(0.89 V) and Fe(3+/2+) (0.77 V) with Ce(4+/3+) (1.61 V), Pd ion accelerates the electron transfer from Fe(2+) to Ce(4+) in Ce(0.65)Fe(0.33)Pd(0.02)O(1.815), making it a high oxygen storage material as well as a highly active catalyst for CO oxidation and water gas shift reaction. The activation energy for CO oxidation with Ce(0.65)Fe(0.33)Pd(0.02)O(1.815) is found to be as low as 38 kJ mol(-1). Ce(0.67)Fe(0.33)O(1.835) and Ce(0.65)Fe(0.33)Pd(0.02)O(1.815) have also shown high activity for the water gas shift reaction. CO conversion to CO(2) is 100% H(2) specific with these catalysts and conversion rate was found to be as high 27.2 μmoles g(-1) s(-1) and the activation energy was found to be 46.4 kJ mol(-1) for Ce(0.65)Fe(0.33)Pd(0.02)O(1.815).     

Ambipolar hexa-peri-hexabenzocoronene-fullerene hybrid materials

A new class of self-assembling hexa-peri-hexbenzocoronene (HBC)-fullerene hybrid materials has been synthesized and characterized. Photoluminescence experiments indicate that energy transfer processes can be tuned in these donor-acceptor systems by varying the length and nature of the linker group. In preliminary device testing, ambipolar charge transport behavior is observed in organic field effect transistors, while single active component organic photovoltaic devices consisting of these materials achieved a maximum external quantum efficiency of 30%.     

Photoinduced ligand transformations in a ruthenium complex of dimethoxytetrapyridotetraazapentacene

The dinuclear ruthenium(II) complex [(phen)(2)Ru(tatpOMe)Ru(phen)(2)](4+) (2(4+); phen is 1,10-phenanthroline and tatpOMe is 10,21-dimethoxy-9,10,20,33-tetraazatetrapyrido[3,2-a:2'3'-c:3',2'-l:2',3'-n]pentacene) has been synthesized and characterized by (1)H NMR, ESI mass spectroscopy and elemental analysis. Loss of methoxy group from bridging ligand of complex 2(4+) due to irradiation is observed by (1)H NMR and photochemistry. The interrelated electronic properties UV-Vis, electrochemistry, photochemistry and molecular orbital calculation are analyzed and discussed on the bridging ligand of the complex 2(4+).     

Quantitative evaluation of benzene, toluene, and xylene in the larvae of Drosophila melanogaster by solid-phase microextraction/gas chromatography/mass spectrometry for potential use in toxicological studies

A simple, rapid, and solvent-free method for quantitative determination of benzene, toluene, and Xylene in exposed Drosophila larvae was developed using headspace solid-phase microextraction (HS-SPME) coupled to GC/MS. Larvae fed on standard Drosophila food mixed with benzene, toluene, and Xylene for 48 h were homogenized in Milli-Q water. Extraction of benzene, toluene, and Xylene was performed at 65 degrees C for 30 min on the SPME fiber (silica-fused). Subsequently, the fiber was desorbed in the GC injection port, followed by GC/MS analysis in the selected-ion monitoring mode. An external calibration curve was used for the quantification of benzene, toluene, and Xylene in the exposed organism. Recoveries were in the range of 78-82% (intraday) and 76-81% (interday) in larvae, and 91-96% (intraday) and 87-92% (interday) in the diet. LOD with an S/N of 3:1 and LOQ with an S/N of 10:1 were in the range of 0.01-0.023 and 0.034-0.077 microg/L, respectively. Percent RSD values for benzene, toluene, and Xylene were in the range of 0.50-0.81 (intraday) and 0.89-1.23 (interday) for retention time, and 2.16--3.85 (intraday) and 2.99-4.95 (interday) for peak concentration, showing good repeatability. This method was sensitive enough to quantitate benzene, toluene, and Xylene in small exposed organisms like Drosophila larvae. The SPME/GC/MS method developed may have wider applications in various in vivo toxicological studies.     

Synthesis and spectral study of biologically active macrocyclic complexes of divalent transition metal ions

The condensation reaction of succinyldihydrazide with glyoxal in the presence of divalent metal ions (1: 1: 1) results in the formation of the complexes of type [M(C₆H₈N₄O₂)X₂], where M = Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and X = Cl⁻, NO₃⁻, CH₃COO⁻. The complexes have been characterized with the aid of elemental analyses, conductance measurements and electronic, NMR, infrared spectral studies. On the basis of these studies, a six-coordinated distorted octahedral geometry in which two nitrogen and two carbonyl oxygen atoms are suitably placed for coordination toward metal ion, has been proposed for all the complexes. The complexes were tested for their in vitro antibacterial activity. Some of the complexes showed remarkable antibacterial activities against some selected bacterial strains.     

Zinc(II) selective poly(vinyl chloride) membrane ISE using a macrocyclic compound 1,12,14-triaza-5,8-dioxo-3(4),9(10)-dibenzoylcyclopentadeca-1,12,14-triene as neutral carrier

The potentiometric response characteristics of zinc ion selective PVC-based membrane electrode employing 1,12,14-triaza-5,8-dioxo-3(4),9(10)-dibenzoyl-1,12,14-triene as an inophore was investigated. The proposed electrode exhibits a Nernstian behavior with a slope of 29.2 ± 0.4 mV per decade with a working concentration range of 1.3 × 10^?7–1.0 × 10^?1 mol L^?1 and a detection limit of 1.0 × 10^?8 mol L^?1. The membrane having the composition as TDODBCPT:O-NPOE:PVC:OA; 7:57:30:6 wt.% exhibits the best results. It has a fast response time of 7 s and can be used for at least 100 days without any considerable divergence in potential. The proposed electrode show good discrimination of Zn²⁺ ion from diverse ions. The potential response remains constant over a pH range of 3.5–9.2. The electrode found well work under laboratory conditions. The proposed sensor directly used for determination of zinc ions in human hair sample, wastewater and an indicator electrode with EDTA titration.