An autocatalytic chromogenic and fluorogenic photochemical reaction controlled by nucleic acids

The autocatalytic photochemical reaction, which is potentially controlled by any selected nucleic acid, is highly sequence specific and not inhibited by its products, was developed. This reaction generates colored and fluorescent products, which can be monitored by the naked eye.     

Coordination modes of 1-allyl benzotriazole: synthesis and characterization of cobalt(II), nickel(II), copper(II), copper(I) and silver(I) complexes

Summary The synthesis and coordination behaviour of 1-allylbenzotriazole (ABT), containing both -donating heterocyclic ring nitrogen(s) and a -bonding olefinic group, has been studied by complexation with Co^II, Ni^II, Cu^II, Cu^I and Ag^I salts. The solid complexes M(ABT)₂X₂ (M=Co, Ni or Cu and X=a counterion) and M(ABT)X (M=Cu or Ag and X=Br, I, or NO₃) have been characterised by¹H-n.m.r. (representative Cu^I species) and other physical data. Different modes coordination for the title ligand have been proposed based upon i.r. data which indicate the participation of a -donating ring nitrogen only in complexes with bivalent metal salts, and the involvement of both the ring nitrogen and the allylic olefinic component in bonding to a monovalent metal ion.¹H-n.m.r. data are qualitatively commensurate with participation of the allyl group in monovalent metal complexes.     

Performance enhancement of phosphoric acid fuel cell using phosphosilicate gel based electrolyte

Replacement of phosphoric acid electrolyte by phosphosilicate gel based electrolytes is proposed for performance enhancement of phosphoric acid fuel cell(PAFC).Phosphosilicate gel in paste form and in powder form is synthesized from tetraethoxysilane and orthophosphoric acid using sol-gel method for two different P/Si ratio of 5 and 1.5 respectively.Replacement of phosphoric acid electrolyte by phosphosilicate gel paste enhances the peak power generation of the fuel cell by 133% at 120 ℃ cell temperature;increases the voltage generation in the ohmic regime and extends the maximum possible load current.Polyinyl alcohol(PVA) is used to bind the phosphosilicate gel powder and to form the hybrid crosslinked gel polymer electrolyte membrane.Soaking the membrane with phosphoric acid solution,instead of that with water improves the proton conductivity of the membrane,enhances the voltage and power generation by the fuel cell and extends the maximum possible operating temperature.At lower operating temperature of 70 ℃,peak power produced by phosphosilicate gel polymer electrolyte membrane fuel cell(PGMFC) is increased by 40% compared to that generated by phosphoric acid fuel cell(PAFC).However,the performance of composite membrane diminishes as the cell temperature increases.Thus phosphosilicate gel in paste form is found to be a good alternative of phosphoric acid electrolyte at medium operating temperature range while phosphosilicate gel-PVA composite offers performance enhancement at low operating temperatures.     

Extraction of Residues of Dyfonate-ring-14C from Soil

Abstract

Residues of Dyfonate-ring-¹⁴C were extracted from a clay loam soil with various solvents under a variety of conditions. Recovery of radioactivity from the soil was not related to the polarity (dipole moment) or the dielectric constant of the solvents. Commonly used solvents such as acetone, methanol, ethanol, and hexane/acetone (1:1) extracted only 28, 44, 27, and 25%, respectively, of the residues from the air-dried soil. The extraction efficiencies were increased to 46, 60, 54, and 49%, respectively, when 20% water was added to the soil prior to extraction with these solvents. The amount of water added to the soil and time of contact with water also affected the recovery of radioactivity from the soil. Any of the solvents or methods investigated failed to recover more than 60% of the radioactivity in the soil, indicating that residues of Dyfonate were strongly bound to the soil and were difficult to recover.     

Isochronicity and limit cycle oscillation in chemical systems

Chemical oscillation is an interesting nonlinear dynamical phenomenon which arises due to complex stability condition of the steady state of a reaction far away from equilibrium which is usually characterised by a periodic attractor or a limit cycle around an interior stationary point. In this context Lienard equation is specifically used in the study of nonlinear dynamical properties of an open system which can be utilized to obtain the condition of limit cycle. In conjunction with the property of limit cycle oscillation, here we have shown the condition for isochronicity for different chemical oscillators with the help of renormalisation group method with multiple time scale analysis from a Lienard system. When two variable open system of equations are transformed into a Lienard system of equation the condition for limit cycle and isochronicity can be stated in a unified way. For any such nonlinear oscillator we have shown the route of a dynamical transformation of a limit cycle oscillation to a periodic orbit of centre type depending on the parameters of the system.     

Chromium complexes of an isomeric N-donor ligand, 2-[(N-arylamino)phenylazo]pyridine: amination reactions,X-ray structure,and redox properties

The chromium chemistry of two positional isomers of the ligand 2-[(N-arylamino)phenylazo]pyridine (HL(1)and HL(2)) are described. While the ligand HL(1) coordinates as a bischelating tridentate N,N,N-donor, [L(1)](-), with deprotonation of the amine nitrogen, its isomer HL(2) coordinates as a neutral bidentate N,N-donor. The amine nitrogen in this case remains protonated. Thus the reaction of CrCl(3).nH(2)O with HL(1) produced the brown cationic complex, [Cr(L(1))(2)](+), [1](+). The representative X-ray structure of [1a](ClO(4)) is reported. The two azo nitrogens of the anioinc tridentate ligand approach the metal center closest with Cr(1)-N(azo) av 1.862(6) A. There is a significant degree of ligand backbone conjugation in the coordinated ligands, which resulted in shortening of the C-N distances and also in lengthening of the diazo (N=N) distances. Two synthetic approaches for the synthesis of chromium complexes of HL(2) are investigated. The first approach is based on the substitution reaction, wherein all the coordinated CO ligands of Cr(CO)(6) were completely substituted by the three bidentate HL(2) ligands to produce a violet complex [Cr(HL(2))(3)]. The second approach is based on para-amination reaction of coordinated 2-(phenylazo)pyridine (pap). Thus the reaction of an inert complex, [CrCl(2)(pap)(2)], with ArNH(2) yields a mixed ligand complex, [CrCl(2)(pap)(HL(2))], 3. In this reaction one of the two coordinated pap ligands in [CrCl(2)(pap)(2)] undergoes amination at the para carbon (with respect to the diazo function) to yield HL(2) in situ. This metal-promoted transformation is authenticated by the X-ray structure determination of a representative complex, [CrCl(2)(pap)(HL(2a))], 3a. Notable differences in bond distances along the ligand backbones of the two coordinated ligands in 3a indicate different levels of metal-ligand overlap in this complex. All the chromium complexes of HL(2) are characterized by their intense blue-violet color. The frequencies of the visible range transitions in these complexes linearly correlate with the Hammett's substitution constant. Intraligand charge-transfer transitions in the visible region are believed to be responsible for the intense color. Redox properties of all these complexes are reported.