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61.
Anil K. Singh Ram Kishan Vijay Bahadur Narayanasamy Vijayan Vadivelu Balachandran Hemandra K. Tiwari Brajendra K. Singh Brijesh Rathi 《Journal of Physical Organic Chemistry》2014,27(6):490-497
Novel phthalimides ( 1 , 2 , 3 ) possessing variability of cyclic amines have been synthesized and characterized by analytical and spectroscopic techniques. Phthalimide 1 and 2 crystallized in a triclinic system with space group Pī; however, an orthorhombic system with a chiral space group of P212121 was observed for 3 possessing piperidine cyclic amine. The hydrogen atoms attached to the central chiral carbon were oriented anti to each other resulting in minimum steric repulsion. The occurrence of C–H···O hydrogen bonds in 1 , 2 , 3 enabled the building of several supramolecular structures. Hyperpolarizability 197.6096 Debye Å2 calculated for 1 was found to be higher than the hyperpolarizabilities, 138.0836 and 165.2521 Debye Å2 measured for 2 and 3 , respectively. Subsequently, phthalimides ( 1 , 2 , 3 ) were assessed for second harmonic generation (SHG) response, and a negligible response was recorded for 1 and 2 ; however, 3 showed a significant response of 14.2 mV. In addition to acentric structure, helical structural motifs identified in 3 could be responsible for its enhanced SHG response. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
62.
D. Santhosh Kumar K. P. Jayakumar S. Balachandran 《Journal of Physical Organic Chemistry》2010,23(8):783-788
1,2‐Diphenylethyl chloride undergoes solvolysis by SN1 mechanism in aqueous organic solvents. The α‐phenyl group of 1,2‐diphenylethyl chloride enters into conjugation with the developing carbocationic centre. The β‐phenyl group on the other hand was unable to extend its conjugation via neighbouring group participation due to steric inhibition of resonance in the formation of non‐classical carbocation. 1,2‐Diphenylethyl chloride thus behaves similar to 1‐phenylethyl chloride in its solvolysis pattern. The solvolytic rate studies of chloride and methanesulphonate of 1,2‐diphenylethyl alcohol in various aqueous organic solvents show that the dispersion observed in the Winstein–Grunwald plot is not due to a change in leaving group but due to the difference in solvation requirements of aromatic and aliphatic groups. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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Krishnakumar V Balachandran V 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,63(2):464-476
FT-IR and FT-Raman spectra of 2-hydroxy-3-methoxy-5-nitrobenzaldehyde (HMN) and 2-methoxy-1-naphthaldehyde (MN) have been recorded in the regions 4000-400 cm(-1) and 3500-100 cm(-1), respectively. The molecular structure, conformational stability, geometry optimization, vibrational frequencies have been investigated. The total energy calculations of HMN and MN were tried for various possible conformers. The spectra were interpreted with the aid of normal coordinate analysis based on density functional theory (DFT) using B3LYP/6-31G* and B3LYP/6-311+G** level and basis set combinations and was scaled using various scale factors yielding good agreement between observed and calculated frequencies. The infrared and Raman spectra were also predicted from the calculated intensities. Comparison of the simulated spectra with the experimental spectra provides important information about the ability of the computational method to describe the vibrational modes. 相似文献
67.
In this paper we prove a result on the existence and global attractivity of solutions of a nonlinear functional integral equations with deviating arguments. The investigations are placed in the Banach space of real functions defined, continuous and bounded on the real half-axis. The main tool used in consideration is a fixed point theorem of Krasnosel’skii type. A few examples illustrating the obtained results are also included. 相似文献
68.
The electrical conductivity of polycrystalline CaTiO3 was measured over the temperature range 800–1100°C while in thermodynamic equilibrium with oxygen partial pressures from 10?22 to 100 atm. The data were found to be proportional to the power of the oxygen partial pressure for the oxygen pressure range 10?16 – 10?22 atm, proportional to for the oxygen pressure range 10?8 – 10?15 atm, and proportional to for the oxygen pressure range greater than 10?4 atm. The region of linearity where the electrical conductivity varies as power of PO2 increased as the temperature was decreased. The observed data are consistent with the presence of small amounts of acceptor impurities in CaTiO3. The band-gap energy (extrapolated to zero temperature) was estimated to be 3.46 eV. 相似文献
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Impact Dynamics in Milling of Thin-Walled Structures 总被引:5,自引:0,他引:5
The development of reliable high-speed spindles and motioncontrol systems has led to an increase in the industrial use ofhigh-speed milling. One of the primary applications of this newtechnology is the manufacture of thin-walled aluminum components foraircraft. The flexibility of the tools and workpieces, the high spindlefrequencies, and the inherent impact nonlinearities in the millingprocess can lead to complicated dynamic tool-workpieceinteractions. An experiment was constructed to study the vibrations ofa thin-walled part during milling. Time series, power spectra,autocorrelations, auto-bispectra, and phase portraits were examined.From this data, it is inferred that stiffness and damping nonlinearitiesdue to the intermittent cutting action have a pronounced effect on thedynamics of the workpiece. Delay space reconstructions and pointwisedimension calculations show that the associated motions arecharacterized by a fractal geometry. The auto-bispectra suggestquadratic phase coupling among the spectral peaks associated with thecutter frequency. A mechanics-based model with impact-nonlinearities wasdeveloped to explain the observed results. The predicted results agreewell with the experimental observations. The model predictions indicatethat aperiodic motions are possible over a large range ofcontrol-parameter values. These analytical and experimental results haveimplications for the prediction and control of vibrations in milling. 相似文献