Unusual photodimerization of 7-fluoro-4-methylcoumarin and 6-fluoro-4-methylcoumarin in the solid state

Photodimerization of 7-fluoro-4-methylcoumarin 1 is topochemical while 6-fluoro-4-methylcoumarin 2 does not lead to the expected product based on the topochemical principles. Compound 1 yield an anti-MT photodimer with a lower dimer conversion while compound 2 results in a syn-HH photodimer. The packing features of 1, 2 and 2a (the photodimer of 2) have been unequivocally established by single crystal X-ray diffraction studies. The rationale for the significant lower dimer conversion in 1 is provided. The defect induced dimerization reaction in 2 as a function of temperature is analyzed which verifies that the reaction proceeds with an induction period. The details of the interactions involving fluorine are analyzed.

Solid state stacked trimers of 1,10-phenanthroline in a supramolecular tubular motif of C-methyl calix[4]resorcinarene

The self-assembly of bidentate ligand, 1,10-phenanthroline with C-methyl calix[4]resorcinarene (CMCR) in presence of coumarin results in a unique trimer stacking arrangement of phenanthroline molecules in a nanotubular motif generated by the supramolecular assembly of the host.

Ground and Excited State Intramolecular Proton Transfer in Salicylic Acid: an Ab Initio Electronic Structure Investigation

Energetics of the ground and excited state intramolecular proton transfer in salicylic acid have been studied by ab initio molecular orbital calculations using the 6-31G** basis set at the restricted Hartree-Fock (RHF) and configuration interaction-single excitation (CIS) levels and also using the semiempirical method AM1 at the RHF level as well as with single and pair doubles excitation configuration interaction spanning eight frontier orbitals (PECI = 8). The ab initio potential energy profile for intramolecular proton transfer in the ground state reveals a single minimum corresponding to the primary form, in the first excited singlet state, however, there are two minima corresponding to the primary and tautomeric forms, separated by a barrier of similar to 6 kcal/mol, thus accounting for dual emission in salicylic acid. Electron density changes with electronic excitation and tautomerism indicate no zwitterion formation. Changes in spectral characteristics with change in pH, due to protonation and deprotonation of salicylic acid, are also accounted for, qualitatively. Although the AM1 calculations suggest a substantial barrier for proton transfer in the ground as well as the first excited state of SA, it predicts the transition wavelength in near quantitative accord with the experimental results for salicylic acid and its protonated and deprotonated forms.

Identification of the nature of platinum related midgap state in silicon by deep level transient spectroscopy

In this article, we present the detailed investigations on platinum related midgap state corresponding to E-c -0.52 eV probed by deep level transient spectroscopy. By irradiating the platinum doped samples with high-energy (1.1 MeV) gamma rays, we observed that the concentration of the midgap state increases and follows a square dependence with irradiation dose. However, the concentration of the acceptor corresponding to E-c -20.28 eV remained constant. Furthermore, from the studies on passivation by atomic hydrogen and thermal reactivation, we noticed that the E-c -0.52 eV level reappears in the samples annealed at high temperatures after hydrogenation. The interaction of platinum with various defects and the qualitative arguments based on the law of mass action suggest that the platinum related midgap defect might possibly correspond to the interstitial platinum-divacancy complex (V-Pt-V).

Implicit and multigrid procedures for steady-state computations with upwind algorithms

A computational study for the convergence acceleration of Euler and Navier-Stokes computations with upwind schemes has been conducted in a unified framework. It involves the flux-vector splitting algorithms due to Steger-Warming and Van Leer, the flux-difference splitting algorithms due to Roe and Osher and the hybrid algorithms, AUSM (Advection Upstream Splitting Method) and HUS (Hybrid Upwind Splitting). Implicit time integration with line Gauss-Seidel relaxation and multigrid are among the procedures which have been systematically investigated on an individual as well as cumulative basis. The upwind schemes have been tested in various implicit-explicit operator combinations such that the optimal among them can be determined based on extensive computations for two-dimensional flows in subsonic, transonic, supersonic and hypersonic flow regimes. In this study, the performance of these implicit time-integration procedures has been systematically compared with those corresponding to a multigrid accelerated explicit Runge-Kutta method. It has been demonstrated that a multigrid method employed in conjunction with an implicit time-integration scheme yields distinctly superior convergence as compared to those associated with either of the acceleration procedures provided that effective smoothers, which have been identified in this investigation, are prescribed in the implicit operator.

State of Charge of Lead Acid Battery

Lead acid batteries are used in hybrid vehicles and telecommunications power supply. For reliable operation of these systems, an indication of state of charge of battery is essential. To determine the state of charge of battery, current integration method combined with open circuit voltage, is being implemented. To reduce the error in the current integration method the dependence of available capacity as a function of discharge current is determined. The current integration method is modified to incorporate this factor. The experimental setup built to obtain the discharge characterstics of the battery is presented.

Denoising neural data with state-space smoothing: Method and application

Neural data are inevitably contaminated by noise. When such noisy data are subjected to statistical analysis, misleading conclusions can be reached. Here we attempt to address this problem by applying a state-space smoothing method, based on the combined use of the Kalman filter theory and the Expectation–Maximization algorithm, to denoise two datasets of local field potentials recorded from monkeys performing a visuomotor task. For the first dataset, it was found that the analysis of the high gamma band (60–90 Hz) neural activity in the prefrontal cortex is highly susceptible to the effect of noise, and denoising leads to markedly improved results that were physiologically interpretable. For the second dataset, Granger causality between primary motor and primary somatosensory cortices was not consistent across two monkeys and the effect of noise was suspected. After denoising, the discrepancy between the two subjects was significantly reduced.

High-Pressure Magnetic-Susceptibility Studies of Spin-State Transaction

High-pressure magnetic susceptibility measurements have been carried out on Fe(dipy)2(NCS)2 and Fe(phen)2(NCS)2 in the pressure range 1–10 kbar and tempeature range 80–300 K in order to investigate the factors responsible for the spin-state transitions. The transitions change from first order to second or higher order upon application of pressure. The temperature variation of the susceptibility at different pressures has been analysed quantitatively within the framework of available models. It is shown that the relative magnitudes of the ΔG0 of high-spin and low-spin conversion and the ferromagnetic interaction between high-spin complexes determines the nature of the transition.

A thermal molecular migration in the solid-state - structures of isomeric 5-amino-4-(2,6-dichlorophenyl)-1-(2-nitrophenyl)-1h-1,2,3-triazole (yellow form i) and 4-(2,6-dichlorophenyl)-5-(2-nitroanilino)-2h-1,2,3-triazole (red form-ii), c14h9cl2n5o2

Yellow form (I): Mr= 350.09, monoclinic, P2Jn, Z--4, a=9.525(1), b=14.762(1), c= 11.268(1),/t, fl= 107.82 (1) o , V= 1508.3 A 3 , Din(flotation in aqueous KI)= 1.539 (2), D x= 1.541 (2) g cm -3, #(Cu Ka, 2 = 1.5418 A) = 40.58 cm -~, F(000) = 712, T= 293 K, R = 8.8% for 2054 significant refections. Red form (II): Mr= 350.09, triclinic, Pi, Z=2, a=9.796(2), b= 10.750 (2), c= 7.421 (1)A, a= 95.29 (2), fl= 0108-2701/84/111901-05501.50 70.18 (1), y = 92-.76 (2) °, V= 731.9 A 3, Din(flotation in KI) = 1.585 (3), D x = 1.588 (3) g cm -3, ~t(Cu Ka, 2 = 1.5418/~) = 40.58 cm -1, F(000) = 356, T=293 K, R = 5.8% for 1866 significant reflections. There are no unusual bond distances or angles. The triazole and two phenyl rings are planar. On the basis of packing considerations the possibility of intermolecular interactions playing a role in the reactivity of the starting material is ruled out.

Initiation Reactions in Thermal Polymerization of Vinyl Monomers in the Molten State

Evidence of the initiation process during uncatalyzed thermal polymerization of vinyl monomers is presented. DSC studies reveal a prominent endothermic effect just before the polymerization exotherm, which is substantiated by the identification of the free radicals produced in the initiation by a quick quenching technique and subsequent detection by ESR at low temperatures.

Steady state optimization of an ammonia reactor

A hybrid simulation technique for identification and steady state optimization of a tubular reactor used in ammonia synthesis is presented. The parameter identification program finds the catalyst activity factor and certain heat transfer coefficients that minimize the sum of squares of deviation from simulated and actual temperature measurements obtained from an operating plant. The optimization program finds the values of three flows to the reactor to maximize the ammonia yield using the estimated parameter values. Powell's direct method of optimization is used in both cases. The results obtained here are compared with the plant data.

Vermicular graphite cast iron current state of the art

Vermicular graphite cast iron is a new addition to the family of cast irons. Various methods for producing vermicular graphite cast iron are briefly discussed in this paper. The mechanical and physical properties of cast irons with vermicular graphite have been found to be intermediate between those of gray and ductile irons. Other properties such as casting characteristics, scaling resistance, damping capacity and machinability have been compared with those of gray and ductile irons. Probable applications of vermicular graphite cast irons are suggested.

State space formulation of ammonia reactor dynamics

The specific objective of this paper is to develop a state space model of a tubular ammonia reactor which is the heart of an ammonia plant in a fertiliser complex. A ninth order model with three control inputs and two disturbance inputs is generated from the nonlinear distributed model using linearization and lumping approximations. The lumped model is chosen such that the steady state temperature at the exit of the catalyst bed computed from the simplified state space model is close enough to the one computed from the nonlinear steady state model. The model developed in this paper is very useful for the design of continuous/discrete versions of single variable/multivariable control algorithms.

State of Charge of Lead Acid Battery

Lead acid batteries are used in hybrid vehicles and telecommunications power supply. For reliable operation of these systems, an indication of state of charge of battery is essential. To determine the state of charge of battery, current integration method combined with open circuit voltage, is being implemented. To reduce the error in the current integration method the dependence of available capacity as a function of discharge current is determined. The current integration method is modified to incorporate this factor. The experimental setup built to obtain the discharge characterstics of the battery is presented

Spin-state equilibria in the LCoO3 system from 59Co NMR

Spin-state equilibria in the whole set of LCoO3 (where L stands for a rare-earth metal or Y) have been investigated with the use of 59Co NMR as a probe for the polycrystalline samples (except Ce) in the temperature interval 110-550 K and frequency range 3- 11.6 MHz. Besides confirming the coexistence of the high-spin—low-spin state in this temperature range, a quadrupolar interaction of ∼0.1 -0.5 MHz has been detected for the first time from 59Co NMR. The NMR line shape is found to depend strongly on the relative magnitude of the magnetic and quadrupolar interactions present. Analysis of the powder pattern reveals two basically different types of transferred hyperfine interaction between the lighter and heavier members of the rare-earth series. The first three members of the lighter rare-earth metals La, Pr (rhombohedral), and Nd (tetragonal), exhibit second-order quadrupolar interaction with a zero-asymmetry parameter at lower temperatures. Above a critical temperature TS (dependent on the size of the rare-earth ion), the quadrupolar interaction becomes temperature dependent and eventually gives rise to a first-order interaction thus indicating a possible second-order phase change. Sm and Eu (orthorhombic) exhibit also a second-order quadrupolar interaction with a nonzero asymmetry parameter ((η∼0.47)) at 300 K, while the orthorhombic second-half members (Dy,..., Lu and Y) exhibit first-order quadrupolar interaction at all temperatures. Normal paramagnetic behavior, i.e., a linear variation of Kiso with T-1, has been observed in the heavier rare-earth cobaltites (Er,..., Lu and Y), whereas an anomalous variation has been observed in (La,..., Nd)CoO3. Thus, Kiso increases with increasing temperature in PrCoO3 and NdCoO3. These observations corroborate the model of the spin-state equilibria in LCoO3 originally proposed by Raccah and Goodenough. A high-spin—low-spin ratio, r=1, can be stabilized in the perovskite structure by a cooperative displacement of the oxygen atoms from the high-spin towards the low-spin cation. Where this ordering into high- and low-spin sublattices occurs at r=1, one can anticipate equivalent displacement of all near-neighbor oxygen atoms towards a low-spin cobalt ion. Thus the heavier LCoO3 exhibits a small temperature-independent first-order quadrupolar interaction. Where r<1, the high- and low-spin states are disordered, giving rise to a temperature-dependent second-order quadrupolar interaction with an anomalous Kiso for the lighter LCoO3.