Colorimetric Determination of Seleniumin Various Environmental Samples

A new reagent system using rhodamine‐B dye for the determination of selenium is described. The method is based on the reaction of selenium with acidified potassium iodide to liberate iodine. The liberated iodine bleaches the pink colour rhodamine‐B, which is measured at 555 nm. Beer's law is obeyed over the concentration range of 1–10 μg of selenium final solution volume of 25 mL (0.04–0.4 ppm) and the apparent molar absorptivity and Sandell's sensitivity was found to be 1.96× 10⁵ l mol^?1 cm^?1 and 0.0004 μg cm^?2, respectively. The method is simple, sensitive, and selective and is satisfactorily applied to micro‐level determination of selenium in various environmental and cosmetic samples.     

Electro-osmotically actuated oscillatory flow of a physiological fluid on a porous microchannel subject to an external AC electric field having dissimilar frequencies

Electro-osmotic flow of a physiological fluid with prominent micropolar characteristics, flowing over a microchannel has been analyzed for a situation, where the system is subject to the action of an external AC electric field. In order to account for the rotation of the micro-particles suspended in the physiological fluid, the fluid has been treated as a micropolar fluid. The microchannel is considered to be bounded by two porous plates executing oscillatory motion. Such motion of the plates will normally induce oscillatory flow of the fluid. The governing equations of the fluid include a second-order partial differential equation depicting Gauss’s law of electrical charge distributions and two other partial differential equations of second order that arise out of the laws of conservation of linear and angular momenta. These equations have been solved under the sole influence of electrokinetic forces, by using appropriate boundary conditions. This enabled us to determine explicit analytical expressions for the electro-osmotic velocity of the fluid and the microrotation of the suspended micro-particles. These expressions have been used to obtain numerical estimates of important physical variables associated with the oscillatory electro-osmotic flow of a blood sample inside a micro-bio-fluidic device. The numerical results presented in graphical form clearly indicate that the formation of an electrical double layer near the vicinity of the wall causes linear momentum to reduce. In contrast, the angular momentum increases with the enhancement of microrotation of the suspended microparticles. The study will find important applications in the validation of results of further experimental and numerical models pertaining to flow in micro-bio-fluidic devices. It will also be useful in the improvement of the design and construction of various micro-bio-fluidic devices.     

Processable Heat-Resistant Polymers. IX. Synthesis and Properties of Polyamideimide from N-(p-Carboxy Phenyl) Trimellitimide and p,p′-Di-(amino Phenyl) Sulfone

A novel polyamideimide was synthesized by reacting p,p′-di-(amino phenyl) sulfone and N-(p-carboxy phenyl) trimellitimide or its diacid chloride derivative. The polymer was found to be soluble in highly polar solvents. The polymer was characterized by elemental analyses and IR spectrum. It is found to be amorphous and of low molecular weight. The polymer is fairly thermostable, having a T of 210–220°C. Thermogravimetric determination revealed that the polymer underwent 17% weight loss at 375°C in air. The dielectric constant of the polymer at 1 kHz was 3.74 at 30°C. The electrical conductivity of the polymer was also measured.     

Donor-Acceptor Complexes in Copolymerization. XVIII. Alternating Diene–Dienophile Copolymers. 1. Conjugated Diene–Maleic Anhydride Copolymers through Radical-Catalyzed Polymerization

The copolymerization of isoprene, butadiene, and other conjugated dienes with maleic anhydride was readily initiated in polar solvents by conventional free radical catalysts, including peroxides, hydroperoxides, and azobisisobutyronitrile, at high concentrations or at temperatures at which the catalyst had a half-life of 1 hr or less and the total reaction time was 0.5-1 hr. Decreasing the reaction temperature or the rate of catalyst addition resulted in increased yields of Diels-Alder adduct and decreased yields of copolymer. The molecular weight decreased as the temperature increased. Dioxane and tetrahydrofuran peroxides, obtained by the passage of oxygen or UV irradiation in air, also initiated the copolymerization. The soluble diene-maleic anhydride copolymers were equimolar and alternating, had [n] 0.1-6 (cyclohexanone) and contained 75-95% 1,4 structure according to ozonolysis, titration with IC1 and NMR. The IR spectrum of the butadiene–maleic anhydride copolymer indicated 75-95% cis-1,4, 5-20% trans-1,4 and 0-5% 1,2-vinyl unsaturation. The proposed mechanism of polymerization involves a donor-acceptor (diene-dienophile) interaction generating a ground-state charge transfer complex which is readily converted to the cyclic adduct. Under the influence of radicals the ground-state complex is transformed into an excited complex which undergoes polymerization. High concentrations of radicals are necessary to generate polymerizable excited complexes in competition with adduct formation.     

Layer-by-layer electrostatic assembly with a control over orientation of molecules: anisotropy of electrical conductivity and dielectric properties

While forming layer-by-layer (LbL) electrostatic assembly of a magnetic organic molecule, namely, nickel phthalocyanine (NiPc), we apply a magnetic field. The field orients the magnetic moment of the molecules on a monolayer along the direction of magnetic field. Such an orientation of the molecules is then electrostatically immobilized with a monolayer of a polycation. By repeating the dipping cycle, we form LbL films with planar NiPc molecules facing a particular direction. With NiPc's moment perpendicular to the molecular plane, two types of LbL films were formed: (a) NiPc's molecular plane parallel to the substrate (moment is perpendicular) and (b) molecules perpendicular to the substrate and facing one particular direction, the direction of magnetic field. Such films, with the molecules lying either (a) parallel or (b) perpendicular to the substrate, provide unique systems to study anisotropy of optical, dielectric, and electrical characteristics in these planar organic molecules. The latter film responds to the polarization of incident beam in electronic absorption spectroscopy. Here we show methods to obtain an orientation of molecules in LbL films and study anisotropy of dielectric constant and conductivity of the molecules in ultrathin films.     

Thermally induced solid-state isomerisation and decomposition of 2,2-dimethyl-1,3-propanediamine nikel(II) complexes

Summary Complexes [NiL₃]Br₂·H₂O (L=2,2-dimethyl-1,3-propanediamine), [NiL₂X₂] (X=Cl, Br, NCS, CF₃CO₂, HCCl₂CO₂ or CCl₃CO₂ and X₂=SO₄ or SeO₄) and [NiL(HCCl₂CO₂)₂]·H₂O have been synthesised and their thermal studies have been investigated in the solid state. The complexes, [NiL₂X₂] (X=Cl or Br) and NiLX₂ (X=Cl or HCCl₂CO₂) have been isolated thermally in the solid state. All the complexes possess octahedral geometry. [NiL₂Br₂] and [NiL₂(CF₃CO₂)₂] exist in two interconvertible isomeric forms. H for the conversions were determined. [NiL₂(HCCl₂CO₂)₂] (5) undergoes an irreversible phase transition (178–188°C; H=4.4kJ mol^–1]. NiL(HCCl₂CO₂)₂·H₂O shows an exothermic irreversible phase transition (104–128°C; H=–5.8 kJ mol^–1) after losing water. The phase transitions are assumed to be due to the conformational changes in the chelate ring of diamine.     

The latent fingerprint in mass transport of polycrystalline materials

Herein, a systematic investigation was carried out to reach a rational understanding and to provide information concerning the possible causes for a significant influence of pressure variation in the underlying processes of mass transport in polycrystalline materials. The authors focused their research in solid-state diffusion, a part of the subject “Mass Transport in Solids”. Theories on diffusion are the subject by itself which exists as a latent fingerprint in every text of higher learning in interdisciplinary science. In this research, authors prepared sandwich samples of titanium alloy and stainless steel using nickel as an intermediate metal. The samples were processed at three different levels of bonding pressure (3, 4 and 5 MPa) while bonding temperature and bonding time was maintained at 750 °C and 1 h, respectively, throughout the experiments. It was observed that the net flux of atomic diffusion of nickel atoms into Ti-alloy at TiA/Ni interface increased by ~63 % with the rise in the bonding pressure from 3 to 4 MPa, but decreased by ~40 % with the rise in the bonding pressure from 4 to 5 MPa. At the same time, the net flux of atomic diffusion of nickel atoms into stainless steel at Ni/SS interface increased by ~19 % with the rise in the bonding pressure from 3 to 4 MPa, but increased by ~17 % with the rise in the bonding pressure from 4 to 5 MPa. Here authors showed that the pressure variations have different effects at the TiA/Ni interface and Ni/SS interface, and tried to explain the explicit mechanisms operating behind them. In general for sandwich samples processed irrespective of bonding pressure chosen, the net flux of Ni-atoms diffused into SS is greater than that of the net flux of Ni-atoms diffused in Ti-alloy matrix by four orders of magnitude. The calculated diffusivity of Ni-atoms into Ti-alloy reaches its highest value of ~5.083 × 10^?19 m²/s for the sandwich sample processed using 4-MPa bonding-pressure, whereas the diffusivity of Ni-atoms into SS reaches its peak value of ~1.615 × 10^?14 m²/s for the sample bonded using 5-MPa bonding-pressure.     

On the gelation rate of thermoreversible poly(vinylidene fluoride) gels in glyceryl tributyrate

The gelation rate of poly(vinylidene fluoride) (PVF₂)/glyceryl tributyrate (GTB) system has been measured. It has been analysed with the help of an equation which contains φⁿ and f(T) term where φ is a reduced overlapping concentration and n is analogous to the percolation exponent β in a three-dimensional lattice. f(T) is related to the temperature function of the coil-to-helix transition. Analysis of the gelation rates supports that the three-dimensional percolation is a suitable mechanism in this gelation process and it also indicates that the gelation is caused by coil-to-helix transition followed by their association.