Showing papers by "Indian Association for the Cultivation of Science published in 2002"

Crystallization mechanism of regioregular poly(3‐alkyl thiophene)s

Abstract: The crystallization properties of three regioregular poly(3-alkyl thiophene)s (P3ATs) are studied: poly(3-hexyl thiophene) (P3HT), poly(3-octyl thiophene) (P3OT), and poly(3-dodecyl thiophene) (P3DDT). The morphology of the isothermally crystallized samples is a whisker type. The values of the enthalpy of fusion of ideal crystals (ΔH), determined from the melting point depression in the polymer–diluent system, are 99, 73.6, and 52 J/g for P3HT, P3OT, and P3DDT, respectively. The values of the equilibrium melting point (T), determined from the Hoffman–Weeks extrapolation procedure, are 300, 230, and 180 °C for P3HT, P3OT, and P3DDT, respectively. From the linear extrapolation of the P3AT data, the T and ΔH values of unsubstituted polythiophene are predicted to be 400 °C and 139 J/g, respectively. The crystallization kinetics of these polymers are studied with differential scanning calorimetry, and the Avrami exponents vary between 0.6 and 1.4, indicating one-dimensional heterogeneous nucleation with linear growth. As the P3AT whiskers are produced from the chain-folding process, the Lauritzen–Hoffman growth rate theory is applied to analyze the temperature coefficient of the crystallization rate data. Graphical plots indicate a transition from regime I to regime II during isothermal crystallization for all the P3ATs studied. The fold surface energy and the work of chain folding calculated from the slopes of the graphical plots decrease with an increase in the number of carbon atoms of the side chain. The primary crystallization process of the side-chain crystallization is very fast and is attributed to the zipping effect of the main-chain crystals. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2073–2085, 2002

Study of the thermal behavior of alkali‐treated jute fibers

Abstract: Jute fibers were treated with 5% NaOH solution for 2, 4, 6, and 8 h to study the performance of the fibers as a reinforcing material in the composites. Thermal analysis of the fibers was done by the DTG and DSC technique. The moisture desorption was observed at a lower temperature in the case of all the treated fibers, which might be a result of the increased fineness of the fibers, which provides more surface area for moisture evaporation. The decrease in percentage moisture loss for the fibers treated with alkali for 6 and 8 h could be the result of the increased crystallinity of the fibers. The percentage degradation of the hemicellulose decreased considerably in all the treated fibers, conforming to the fact that the hemicellulose content was lowered on alkali treatment. The decomposition temperature for α-cellulose was lowered to 348°C from 362.2°C for all the treated fibers, and the residual char formation increased to a significant extent. The enthalpy for the thermal degradation of α-cellulose showed a decreasing trend for the fibers treated for 2 and 4 h, which could be caused by the initial loosening of the structure, followed by an increase in the enthalpy value in the case of the 6- and 8-h-alkali-treated fibers resulting from increased crystallinity, as evident from the X-ray diffraction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2594–2599, 2002

Impact fatigue behaviour of vinylester resin matrix composites reinforced with alkali treated jute fibres

Abstract: An impact fatigue study has been made for the first time on 35% jute/vinylester composites containing both untreated and alkali treated fibres. Longer alkali treatment removed the hemicellulose and improved the crystallinity and gave better fibre dispersion. The flexural strength properties of the composites made from treated fibre were superior. 4 h alkali treated jute fibres gave the optimum combination of improved interfacial bonding and fibre strength properties. However this was not reflected in their impact fatigue behaviour. On the contrary, the composites reinforced with 8 h alkali treated fibres displayed superior impact fatigue properties. Here, the fibres suffered catastrophic fracture with microfibrillar pull-out at some places and improved the fatigue resistance property of the composites as evident from SEM micrographs.

Valence delocalization in a mixed-oxidation divanadium (IV, V) complex electrogenerated from its structurally characterized divanadium (V) analogue with a tridentate (ONO) ligand.

Abstract: A new complex containing the {OVv(μ-O)VvO}4+ unit has been synthesized and structurally characterized. Cyclic voltammogram of this complex showed that the two VV centers of the V2O34+ core are found to undergo electrochemical reduction in two distinctly separate steps not observed previously in similar systems. A rare mixed-oxidation state species [L(O)VIVOVV(O)L]- has been electrogenerated from the structurally characterized parent divanadium (V) species in solution state and characterized by IR, EPR, and electronic spectroscopy.

Energy levels and structural properties of compressed hydrogen atom under Debye screening

Abstract: Time dependent variation perturbation calculations have been performed for estimating the transition energies, os- cillator strengths and transition probability values for a few dipole allowed states of compressed hydrogen atom confined in a weakly coupled plasma. The compression is obtained by embedding the atom at the centre of an impenetrable spherical box. The dipole polarizability of the atom is evaluated at each confinement radius with respect to different plasma screening param- eters. The effect of pressure due to spatial confinement on the dipole polarizability and other atomic properties is analyzed. Results obtained are useful for the diagnostic determination of astrophysical and laboratory plasmas and for the calculation of collision rate coefficients needed for computing opacity of stellar envelopes - a quantity of importance in the context of stellar structure and pulsations.

A novel class of interpenetrated 3-D network of a dimeric cupric-tetracarboxylate unit

Abstract: The hydrothermal reaction of Cu(II), fumaric acid and 4,4′-bipyridine (bpy) in equimolar amounts at 160 °C resulted in a new type of two-fold interpenetrating 3-D coordination network composed of tetracarboxylate dicopper(II) units bridged by bipyridine spacers.

A family of mononuclear molybdenum-(VI), and -(IV) oxo complexes with a tridentate (ONO) ligand

Abstract: The salicylhydrazone of anthranilhydrazide (H2L) reacted with MoO2(acac)2 in refluxing alcohols to yield compounds of the general formula MoO2L(ROH) (where R = CH3, C2H5, n-C3H7, n-C4H9). The complex MoO2L(C2H5OH) is found to undergo facile reaction with heterocyclic bases to form MoO2L(Q)-type complexes where Q = pyridine, 4-picoline, imidazole and substituted imidazoles. Single crystal X-ray structural studies on the ligand H2L (1) and the complexes MoO2L(C2H5OH) (2) and MoO2L(Imz) (3) indicate that the free ligand exists in its keto form, but in the two complexes 2 and 3 the ligand coordinates to the MoO22+ core through the enolate oxygen, the phenolate oxygen and the azomethine nitrogen. Reaction of MoO2L(C2H5OH) with PPh3 in CH3CN under dry dinitrogen, in the absence and presence of bipy, produced MoIVOL (2a) (brown) and MoIVOL(bipy) (2b) (green) respectively along with Ph3PO. This reaction is reminiscent of the oxotransfer reaction from the MoO2+2 core of a molybdoenzyme to the substrate PPh3. Complexes 2 and 3 crystallized in the P21/n and P21/c space groups respectively and for both of them Z = 4. The structures clearly show that 2 and 3 have distorted octahedral coordination environments in which the Mo–O(ethanol) bond of 2 and the Mo–N (imidazole) bond of 3 are significantly longer than is usually observed. This is indicative of the weak bonding of ethanol and imidazole to the MoO22+ core and points to the inherent weakness of the sixth coordination position of the coordination polyhedron of the MoO22+ core in MoO2L(C2H5OH) and MoO2L(Imz).

Synthesis and characterization of sol-gel derived ZnS : Mn2+ nanocrystallites embedded in a silica matrix

Abstract: Synthesis and characterization of undoped and Mn2+ doped ZnS nanocrystallites (radius 2–3 nm) embedded in a partially densified silica gel matrix are presented. Optical transmittance, photoluminescence (PL), ellipsometric and electron spin resonance measurements revealed manifestation of quantum size effect. PL spectra recorded at room temperature revealed broad blue emission signal centred at ∼ 420 nm and Mn2+ related yellow-orange band centred at ∼ 590 nm while ESR indicated that Mn in ZnS was present as dispersed impurity rather than Mn cluster.

Review Synthesis of conducting nanowires

Abstract: Work reported on the synthesis of nanowires of different metals/alloys and semiconductors respectively in recent years is reviewed The methods used mostly belong to one of the following categories: chemical, electrodeposition, physical and filling of carbon nanotubes Electrical properties investigated for some of these nanowires indicate quantum mechanical effects to be present Nanodevice fabrication using doped semiconducting nanowires has also been reported

Synthesis, crystal structures and magnetic properties of 1D polymeric [MnIII(salen)N3] and [MnIII(salen)Ag(CN)2] complexes

Abstract: The syntheses, crystal structures and variable temperature (5–300 K) magnetic susceptibility measurements of two salen complexes of manganese(III) [where H2salen = N,N′-bis(salicylidene)-1,2-diaminoethane] having azido and dicyano argentate(I) as bridging ligands are reported. Both complexes belong to one-dimensional systems in which the azido functions as μ-(1,3) and Ag(CN)2− as ⋯NC– Ag–CN⋯ bridging ligands. The azido-bridged compound is antiferromagnetic with an intrachain interaction constant J = −4.52(4) cm−1 (Weng model) or J = −5.19(8) cm−1 (Fisher model), and it is a candidate to observe the Haldane gap in a S = 2 system. The silver cyanide bridged complex shows single ion behaviour of the Mn(III) ion, perhaps in combination with a very weak antiferromagnetic interaction.

Short and stereoselective total synthesis of furano lignans (+/-)-dihydrosesamin, (+/-)-lariciresinol dimethyl ether, (+/-)-acuminatin methyl ether, (+/-)-sanshodiol methyl ether, (+/-)-lariciresinol, (+/-)-acuminatin, and (+/-)-lariciresinol monomethyl ether and furofuran lignans (+/-)-sesamin, (+/-)-eudesmin, (+/-)-piperitol methyl ether, (+/-)-pinoresinol, (+/-)-piperitol, and (+/-)-pinoresinol monomethyl ether by radical cyclization of epoxides using a transition-metal radical source.

Abstract: Intramolecular radical cyclization of suitably substituted epoxy ethers 4a−g using bis(cyclopentadienyl)titanium(III) chloride as the radical source resulted in trisubstituted tetrahydrofurano lignans and 2,6-diaryl-3,7-dioxabicyclo[3.3.0]octane lignans depending on the reaction conditions. The titanium(III) species was prepared in situ from commercially available titanocene dichloride and activated zinc dust in THF. Upon radical cyclization followed by acidic workup, epoxy olefinic ethers 4a−g afforded furano lignans dihydrosesamin 1a, lariciresinol dimethyl ether 1b, acuminatin methyl ether 1e, and sanshodiol methyl ether 1g directly and lariciresinol 1h, acuminatin 1i, and lariciresinol monomethyl ether 1j after removal of the benzyl protecting group by controlled hydrogenolysis of the corresponding cyclized products. The furofuran lignans sesamin 2a, eudesmin 2b, and piperitol methyl ether 2e were also prepared directly by using the same precursors 4a−f on radical cyclization followed by treatment wit...

Surface plasmon resonance in nanocrystalline silver particles embedded in SiO2 matrix

Abstract: Nanocomposite films containing silver particles embedded in SiO2 matrix were prepared by high pressure (~40 Pa) d.c. sputtering technique in an argon plasma on fused silica substrate. Particle size and metal volume fraction were tailored by varying the substrate temperature (Ts~233-300 K) and deposition time (15-240 s). Reduction in size and volume fraction of metal particles culminated in blue-shift of the surface plasmon resonance peak in the optical absorbance spectra of the films. Absence of surface plasmon peak in the absorption spectra below a critical particle size and metal concentration of the nanocomposite films and appearance of sharp absorption edge in the absorbance spectra within the UV-VIS range indicated the semiconducting behaviour of the ultrafine silver particles. Experimental absorbance spectra were theoretically simulated by Mie scattering theory and Maxwell-Garnett effective medium theory.

Three Novel End-to-End Single Azido-Bridged Ferromagnetic Copper(II) Chains: Synthesis, Crystal Structure, and Magnetic Behavior

Abstract: Three new single end-to-end azido-bridged copper(II) chains [Cu(L1)(N3)]n(ClO4)n (1), [Cu(L2)(N3)]n(ClO4)n (2), and [Cu(L3)(N3)]n(ClO4)n (3) using three different tridentate Schiff bases L1, L2, and L3, obtained from condensation of pyridine-2-carbaldehyde with N,N-dimethylethane-1,2-diamine, N,N-diethylethane-1,2-diamine, and 4-(2-aminoethyl)morpholine, respectively, have been synthesized, and their crystal structures have been determined by X-ray diffraction methods. Complex 1, C10H15CuN6ClO4, crystallizes in an orthorhombic system, space group P212121, with a = 7.434(3), b = 12.047(4), c = 17.404(6) A, and Z = 4; complex 2, C12H19CuN6ClO4, crystallizes in an orthorhombic system, space group Pna21, with a = 14.723(5), b = 13.829(5), c = 8.002(5) A, and Z = 4 and complex 3, C12H17CuN6ClO5, crystallizes in an orthorhombic system, space group Pna21, with a = 13.837(15), b = 14.804(2), c = 8.050(4) A, and Z = 4. Each structure consists of a single end-to-end azido-bridged copper(II) 1D chain where each copper(II) center possesses a square pyramidal geometry. Magnetic susceptibility data, measured from 4 to 300 K, show weak ferromagnetic interaction through the end-to-end bridging azido pathway in all the complexes. The magnetic data were fitted to a high temperature series-expansion for a one-dimensional system with S = 1/2 local spin based on the Hamiltonian H = −JΣSi·Si+1 for all the complexes, giving the parameters J = +2.15 cm−1, g = 2.23 for 1, J = +3.61 cm−1, g = 2.16 for 2, and J = +2.06 cm−1, g = 2.17 for 3. This unusual magnetic behavior through the end-to-end bridging azido pathway has been correlated to the structural parameters. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

Solvation Dynamics in Aqueous Polymer Solution and in Polymer−Surfactant Aggregate

Abstract: Solvation dynamics of 2,6-p-toluidinonaphthalene sulfonate (TNS) is studied using picosecond time-resolved emission spectroscopy in an aqueous solution of poly(vinylpyrrolidone) (PVP) and in a polymer−surfactant aggregate consisting of PVP and sodium dodecyl sulfate (SDS). On addition of PVP to an aqueous solution of TNS, the emission quantum yield (φf) of TNS increases about 210 times in 0.75 wt % aqueous solution of PVP. The solvation dynamics of TNS in 0.75 wt % aqueous solution of PVP is found to be biexponential with a major component (85%) of 60 ps and a slower one of 800 ps (15%). The retardation of the solvation dynamics in the dilute polymer solution compared to that in the bulk water is attributed to the restricted movement of water molecules in the vicinity of the polymer chains. The solvation dynamics of TNS in the PVP−SDS aggregate is described by two components, 300 ± 20 ps (55%) and 2500 ± 100 ps (45%). The slower solvation dynamics in PVP−SDS aggregate compared to PVP alone or SDS alone in...

Variational calculations for the energy levels of confined two-electron atomic systems

Abstract: An accurate variational calculation has been performed for the ground-state-energy values of confined two-electron isoelectronic series from He to Ar16+. The confinement is obtained by embedding the ion in an overall charge neutral environment like that of a plasma. The confinement potential is chosen as that of a screened Coulomb potential between charges, obtained from a Debye model. The wave function is expanded in terms of product basis sets involving interparticle coordinates. The energy levels are found to be less bound with an increase of the screening parameter and ultimately become unstable. One- and two-particle moments have been calculated for the first time under such screening. The study is expected to throw new light on the behavior of the energy levels of foreign atoms embedded in an overall neutral environment which can be treated like a plasma.