Spectroscopic and chemical reactivity analysis of D-Myo-Inositol using quantum chemical approach and its experimental verification

Glow discharge conditioning (GDC) has long been accepted as one of the basic wall conditioning techniques for achieving ultrahigh vacuum in an unbaked chamber. As a part of this fundamental experimental study, a test chamber has been fabricated from stainless steel 304 L with its inner surface electropolished on which a detailed investigation has been carried out. Both helium and hydrogen gases have been employed as discharge cleaning medium. The discharge cleaning was carried out at 0.1 A /m ² current density with working pressure maintained at 1.0 × 10 ^-2 mbar. It was experimentally observed that the pump-down time to attain the base pressure ~10 ^-8 mbar was reduced by 62% compared to the unbaked chamber being pumped to this ultimate vacuum. The results were similar irrespective of whether the discharge cleaning medium is either hydrogen or helium. It was also experimentally established that a better ultimate vacuum could be achieved as compared to theoretically calculated ultimate vacuum with the help of discharge cleaning.     

Fitted Mesh Method for a Class of Singularly Perturbed Differential-Difference Equations

This paper deals with a more general class of singularly perturbed boundary value problem for a differential-difference equations with small shifts. In particular, the numerical study for the problems where second order derivative is multiplied by a small parameter $ε$ and the shifts depend on the small parameter $ε$ has been considered. The fitted-mesh technique is employed to generate a piecewise-uniform mesh, condensed in the neighborhood of the boundary layer. The cubic B-spline basis functions with fitted-mesh are considered in the procedure which yield a tridiagonal system which can be solved efficiently by using any well-known algorithm. The stability and parameter-uniform convergence analysis of the proposed method have been discussed. The method has been shown to have almost second-order parameter-uniform convergence. The effect of small parameters on the boundary layer has also been discussed. To demonstrate the performance of the proposed scheme, several numerical experiments have been carried out.     

On-line high-performance liquid chromatography–ultraviolet–nuclear magnetic resonance method of the markers of nerve agents for verification of the Chemical Weapons Convention

This paper details an on-flow liquid chromatography–ultraviolet–nuclear magnetic resonance (LC–UV–NMR) method for the retrospective detection and identification of alkyl alkylphosphonic acids (AAPAs) and alkylphosphonic acids (APAs), the markers of the toxic nerve agents for verification of the Chemical Weapons Convention (CWC). Initially, the LC–UV–NMR parameters were optimized for benzyl derivatives of the APAs and AAPAs. The optimized parameters include stationary phase C₁₈, mobile phase methanol:water 78:22 (v/v), UV detection at 268 nm and ¹H NMR acquisition conditions. The protocol described herein allowed the detection of analytes through acquisition of high quality NMR spectra from the aqueous solution of the APAs and AAPAs with high concentrations of interfering background chemicals which have been removed by preceding sample preparation. The reported standard deviation for the quantification is related to the UV detector which showed relative standard deviations (RSDs) for quantification within ±1.1%, while lower limit of detection upto 16 μg (in μg absolute) for the NMR detector. Finally the developed LC–UV–NMR method was applied to identify the APAs and AAPAs in real water samples, consequent to solid phase extraction and derivatization. The method is fast (total experiment time ∼2 h), sensitive, rugged and efficient.     

To analyse the performance of tapered and MMI assisted splitter on the basis of geographical parameters

A literal model using geometric examination was formulated to calculate the optimum width and length of multimode interference structure used in the 1 × 2 power splitter and plot electric field intensity for input and each output signal. Designing and simulation of the wavelength response of 1 × 2 splitter using Tapered and MMI assisted structure. Mechanism on the critical geographical parameters like length and width of MMI structure, separation distance between output ports ‘S’, arm angle ‘α’ which give the optimum power and electric field intensity for the considered necessary wavelength. Finite difference beam propagation methods have been used to simulate the conventional and tapered MMI device behaviour.     

Design and performance analysis in multiuser optical CDMA systems

The article presents comparative performance analysis of the proposed Optical CDMA system for 32 and 16 users with two dimensional codes. Numerical simulations have been done under interference significant environment, considering noise and dark current at data rates 2.5, 5, 7.5 and 10 Gbps over single mode fiber for transmission distance of more than 270 km. Results illustrate overall good performance, degraded with augment in bit rate and transmission distance, impervious with raise in number of simultaneous active users. Depicts significant performance improvement with inclusion of forward error correction RS (255,239), for low attenuation and chirp factor. It perceived, this is one of the efficient functional techniques for next generation broadband optical networks together with higher security owing to encoding and decoding, as it allow multiple users in the network to access the same fiber channel asynchronously.     

Optical bistability in Coumarin-450 doped polymeric samples

Experimental observations of optical bistability in Coumarin-450 dye molecule entrapped in polymeric (PMMA) host inside Fabry–Perot cavity have been reported. Efforts have been made to demonstrate the nonlinear behavior of optical materials in solid form using 532 nm of Nd: YAG laser. The nonlinearity in terms of optical bistability and excited state absorption (ESA) has been discussed. The nonlinearity in Coumarin-450 dye molecule originated from unique intensity dependence of the complex index of refraction. It has been observed that nonlinear refraction dominates over nonlinear absorption in giving rise to the optical bistability. Nonlinear refractive index in both polymeric and liquid samples has been calculated.     

Carbonylative Suzuki coupling reactions catalyzed by ONO pincer–type Pd(II) complexes using chloroform as a carbon monoxide surrogate

Benzoylhydrazone Schiff base–ligated three new ONO pincer–type palladium(II) complexes, [(PdL¹(PPh₃)] ( 1 ), [(PdL²(PPh₃)] ( 2 ), and [(PdL³(PPh₃)] ( 3 ), were synthesized by the reaction of the respective ligand, N-(2-hydroxybenzylidene)benzohydrazide (HL¹), N-(2-hydroxy-3-methoxybenzylidene)benzohydrazide (HL²), or N-(5-bromo-2-hydroxybenzylidene) benzohydrazide (HL³), with Pd(OAc)₂ and PPh₃ in methanol and isolated as air-stable reddish-orange crystalline solids in high yields (78%–83%). All three complexes were fully characterized by elemental analysis, Fourier-transform infrared spectroscopy, UV–Visible, ¹H nuclear magnetic resonance (NMR), ¹³C{¹H} NMR, and ³¹P{¹H} NMR spectroscopic studies. The molecular structure of all three complexes was established unambiguously by single-crystal X-ray diffraction studies which revealed a distorted square planar geometry of all three complexes. The ONO pincer–type ligands occupied three coordination sites at the palladium, while the fourth site is occupied by the monodentate triphenylphosphine ligand. The catalytic potential of all three complexes was explored in the carbonylative Suzuki coupling of aryl bromides and iodides with arylboronic acids to yield biaryl ketones, using CHCl₃ as the source of carbonyl. The reported protocol is convenient and safe as it obviates the use of carbon monoxide (CO) balloons or pressured CO reactors which are otherwise needed for the carbonylation reactions. The methodology has been successfully applied to the synthesis of two antineoplastic drugs, namely, phenstatin and naphthylphenstatin, in good yields (81% and 85%, respectively). Under the optimized reaction conditions, complex 2 exhibited the best catalytic activity in the carbonylative Suzuki couplings. The reported catalysts have wide reaction scope with good functional group tolerance. All catalysts could be retrieved from the reaction after completion and recycled up to three times with insignificant loss in the catalytic activity.     

Synthesis to spectroscopy of titanium(IV) and zirconium(IV) chelates with biologically active ON donor systems

Summary A new class of 16 organotitanium(IV) and organozirconium(IV) chelates with biologically active monofunctional bidentate semicarbazones having the ON donor system were prepared by reacting 11 and 12 stoichiometric proportions of bis(cyclopentadienyl)titanium(IV) dichloride and bis(cyclopentadienyl)zirconium(IV) dichloride with the appropriate ligand, prepared by condensing heterocyclic ketones and semicarbazide hydrochlorides in presence of NaOAc. Trigonal bipyramidal and octahedral structures have been suggested for the 11 and 12 (ML) complexes of titanium(IV) and zirconium(IV), respectively, on the basis of spectral analyses.     

Transition metal complexes of the 1,2-dihapto-4-cyano-5-amino-pyrazolide ion

Summary Reaction of 4-cyano-5-aminopyrazole, Hcpz, with ammoniacal solutions of metal(I) chlorides yields colorless and insoluble polymeric complexes, [Mcpz]_n [where M=Cu(1) or Ag(2)]. However, pyrazolidebridged dimeric species [M(PPh₃)₂cpz]₂ (3) or(4), soluble in most non-polar solvents, were obtained from the precursor [M(PPh₃)₃X] (X=Cl or NO₃) under similar reaction conditions. The compounds have been characterized using physico-chemical methods and are diamagnetic.