Oxidation of cinnamic acid derivatives: A pulse radiolysis and theoretical study

We introduce an algorithm to solve the secular equation that arises in the time independent multimode expansion of the quadratic vibronic coupling problem in parallel. The implementation can handle expansions of arbitrary length, with the open-ended character of the algorithm achieved through the use of fine grained parallelism to partition the trial vectors. The characteristics of the algorithm are discussed and its utility is illustrated by determining a model photoelectron spectrum of the ethoxy radical (C₂H₅O) using a vibronic expansion involving more than 1 billion vibronic basis states. This calculation also represents the first determination of a photoelectron spectrum obtained using a diabatic Hamiltonian obtained with a recently introduced ab initio surface reshaping procedure.     

Microwave assisted synthesis,spectroscopic and antibacterial studies of titanocene chelates of Schiff bases derived from 3-substituted-4-amino-5-hydrazino-1,2,4-triazoles

The reactions of bis(cyclopentadienyl)titanium(IV) chloride with a new series of Schiff bases (LH₂), derived by condensing 3-(phenyl/2-chlorophenyl/4-nitrophenyl)-4-amino-5-hydrazino-1,2,4-triazoles with salicylaldehyde or 2-hydroxyacetophenone, have been studied both by conventional stirring method and also by using microwave technology. The products of type [(η⁵-C₅H₅)₂Ti(L)] have been isolated in both cases. Tentative structural conclusions are drawn for the reaction products based upon physico-chemical and spectroscopic methods. The ligands behave as dibasic, tetradentate chelating agents and a six-coordinated structure have been assigned to these derivatives. Studies were conducted to assess the growth inhibiting potential of the free Schiff bases and their complexes against various bacterial strains.     

A square pyramidal copper(II) complex of a Schiff base ligand: synthesis,crystal structure,antibacterial and DNA interaction studies

A mononuclear Cu(II) complex [Cu(L)Cl₂] has been synthesized from a tridentate Schiff base ligand, piperidin-2-ylmethyl-pyridin-2-ylmethylene-amine (L). The single-crystal X-ray structure of the complex shows a square pyramidal geometry. The complex was tested against several bacteria and showed good antibacterial activities against almost all of the bacteria. The interactions of the title complex with calf thymus DNA (CT-DNA) have been investigated by electronic absorption and fluorescence spectroscopy, showing that the complex interacts with CT-DNA via partial intercalation.     

Additive role of attapulgite nanoclay on carbonyl iron-based magnetorheological suspension

Attapulgite (ATP), a fibrous nanoclay mineral, was adopted as an additive in this study to improve the sedimentation problem of soft magnetic carbonyl iron (CI)-based magnetorheological (MR) fluids caused by the density mismatch between the CI particles and medium oil. The MR characteristics of the two MR fluid systems with and without ATP were measured and compared using a rotational rheometer under different magnetic field strengths. Scanning electron microscopy indicated that ATP filled the interspaces among the CI particles, explaining the improved dispersion stability of the MR fluid based on the Turbiscan sedimentation measurements. Despite the slight decrease in MR characteristics, the MR fluid with the additive exhibited the typical MR performance of an increase in shear stress in an applied magnetic field.     

Computational study of the mechanism and selectivity of ruthenium-catalyzed hydroamidations of terminal alkynes

Density functional theory calculations were performed to elucidate the mechanism of the ruthenium-catalyzed hydroamidation of terminal alkynes, a powerful and sustainable method for the stereoselective synthesis of enamides. The results provide an explanation for the puzzling experimental finding that with tri-n-butylphosphine (P(Bu)₃) as the ligand, the E-configured enamides are obtained, whereas the stereoselectivity is inverted in favor of the Z-configured enamides with (dicyclohexylphosphino)methane (dcypm) ligands. Using the addition of pyrrolidinone to 1-hexyne as a model reaction, various pathways were investigated, among which a catalytic cycle turned out to be most advantageous for both ligand systems that consists of: (a) oxidative addition, (b) alkyne coordination, (c) alkyne insertion (d) vinyl-vinylidene rearrangement, (e) nucleophilic transfer and finally (f) reductive elimination. The stereoselectivity of the reaction is decided in the nucleophilic transfer step. For the P(ⁿBu)₃ ligand, the butyl moiety is oriented anti to the incoming 2-pyrolidinyl unit during the nucleophilic transfer step, whereas for the dcypm ligand, steric repulsion between the butyl and cyclohexyl groups turns it into a syn orientation. Overall, the formation of E-configured product is favorable by 4.8 kcal mol^–1 (Δ^‡ GSDL) for the catalytic cycle computed with P(Bu)₃ as ancillary ligand, whereas for the catalytic cycle computed with dcypm ligands, the Z-product is favored by 7.0 kcal mol^–1 (Δ^‡ GSDL). These calculations are in excellent agreement with experimental findings.     

Laser Raman spectroscopic study of water in gelatin–surfactant solutions and gels

A Raman spectroscopic study was carried out on water in gelatin at 4% w/v in gel (25 °C) and sol (40–60 °C) states at various concentrations (0.5, 1, 5, 10 and 15 mM) of anionic surfactant, sodium dodecyl sulfate (SDS). The in-phase collective stretching mode vibration of hydrogen-bonded -OH oscillators, centered around 3250 cm⁻¹ in a tetrahedral network of water molecules, was observed to be significantly affected by temperature and the presence of SDS. According to our observation this may be due to the thinning of the hydration water around the gelatin molecules due to strong thermal agitation. The peak center of the collective bands of water decreased linearly with SDS concentration in the gel state which implied that with the increase in concentration of SDS, the -OH oscillators gradually lost their attachment to gelatin chains and were replaced by SDS molecules. Ultimately this resulted in a thinning of the hydration layer around the gelatin and the oscillation frequency of -OH oscillators moved towards 3250 cm⁻¹ at 1 mM SDS concentration resulting in increased coupling of -OH oscillators to form the tetrahedral network at the critical micelle concentration (cmc) of SDS. The variation in the peak amplitudes and the systematic reversal of their trend about the cmc axis was surprising. At 40 °C the amplitude of the peak at 3250 cm⁻¹ increased drastically due to a possible coil expansion by about 7–8% which accommodated more interstitial water into the pseudonetwork leading to an increase in the number of nearest neighbors and for about 6% increase in the C value. However, at the cmc the peak amplitude was observed to be independent of temperature. Continuous shifting of the peak center and full width at half-maxima towards lower values was observed with increasing SDS concentrations in the gel state. Received: 28 September 1998 Accepted in revised form: 8 March 1999     

Experimental investigation on martensitic transformation and fracture morphologies of austenitic stainless steel

Formation and nucleation mechanisms (i.e. γ → ε, γ → α′, γ → deformation twins → ε → α′ and γ → ε → α′) of deformation- induced martensite (DIM) have been studied through analytical transmission electron microscopy (TEM) after tensile deformation of AISI 304LN stainless steel at various strain rates (SR) at room temperature (RT). Quantitative metallography has been employed extensively to assess martensitic transformation (MT) as function of strain and SR. It has been observed that the enhancement of SR during tensile deformation promotes the early formation of DIM, while suppressing its saturation value at fracture. Fracture surface morphologies and dimple geometries (i.e. dimple density, dimple diameter and dimple size distribution) have been quantified through image processing (IP) of tensile fractographs. It is noted that at lower SR, dimple density is high while dimple diameter is smaller, and vice versa. Concomitantly, the strength is noted to be low and ductility is high at lower SR, and vice versa. DIM has been found to be responsible for high dimple density at low SR. At high SR, MT is suppressed and hence low dimple density. The variation in SR dependent MT accounts for the variation in dimple metrics vis-à-vis tensile properties.     

A Reusable Efficient Green Catalyst of 2D Cu-MOF for the Click and Knoevenagel Reaction

[Cu(CPA)(BDC)]_n (CPA = 4-(Chloro-phenyl)-pyridin-4-ylmethylene-amine; BDC = 1,4-benzenedicarboxylate) has been synthesized and structurally characterized by single crystal X-Ray diffraction measurement. The structural studies establish the copper (II) containing 2D sheet with (4,4) square grid structure. The square grid lengths are 10.775 and 10.769 Å. Thermal stability is assessed by TGA, and subsequent PXRD data establish the crystallinity. The surface morphology is evaluated by FE-SEM. The N₂ adsorption−desorption analysis demonstrates the mesoporous feature (∼6.95 nm) of the Cu-MOF. This porous grid serves as heterogeneous green catalyst with superficial recyclability and thermal stability and facilitates organic transformations efficiently such as, Click and Knoevenagel reactions in the aqueous methanolic medium.     

Optimal observable analysis for the decay $$b \rightarrow s$$ plus missing energy

The decay \(b\rightarrow s\nu {\bar{\nu }}\) has received comparatively less attention than the semileptonic decay \(b\rightarrow s\ell ^+\ell ^-\), because neutrinos pass undetected and hence the process offers lesser number of observables. We show how the decay \(b\rightarrow s~+\) invisible(s) can shed light, even with a limited number of observables, on possible new physics beyond the Standard Model and also show, quantitatively, the reach of future B factories like SuperBelle to uncover such new physics. Depending on the operator structure of new physics, different channels may act as the best possible probe. We show, using the optimal observable technique, how almost the entire parameter space allowed till now can successfully be probed at a high-luminosity B factory.