Growth and characterization of single crystal cored fibers of organic nonlinear optical materials

The recent development of several organic materials with large nonlinear susceptibilities, high damage threshold and low melting points encouraged researchers to employ these materials in fiber form to efficiently couple diode laser pumps and obtain enhanced second harmonic generation (SHG). In this paper we report the growth of single crystal cored fibers of 4-nitro-4'-methylbenzylidene aniline, ethoxy methoxy chalcone and (-)2-((alpha) -methylbenzylamino)-5- nitropyridine by inverted Bridgman-Stockbarger technique. The fibers were grown in glass capillaries with varying internal diameters and lengths and were characterized using x-ray and polarizing microscope techniques. The propagation loss at 632.8 nm and 1300 nm were measured and SHG was studied using 1064 nm pump.

Multi frequency interrogation of polypyrrole based gas sensors for organic vapors

Polypyrrole exhibits reversible changes in their direct current resistance on exposure to organic volatiles. However, one needs to employ an array of such sensors to discriminate organic volatiles present in a mixture. Hence, polypyrrole based gas sensor is designed for the detection and discrimination of different organic volatiles. Multi frequency impedance measurement technique is used to detect the organic vapors, such as acetone, ethanol and Isopropyl alcohol, in the gas phase, over a frequency range 10 Hz to 2 MHz. The sensor response is monitored by measuring the changes in its capacitance, resistance and the dissipation factor upon exposure to organic volatiles. It is observed that the capacitive property of the sensor is more sensitive to these volatiles than its resistive property. Each volatile responds to the sensor in terms of dissipation factor at specific frequency and found that the peak magnitude has a linear relationship with their concentrations.

Reaction of diisopropoxytitanium(III) tetrahydroborate with selected organic compounds containing representative functional groups

Diisopropoxytitanium(III) tetrahydroborate, ((PrO)-Pr-1)(2)TiBH4), generated in situ in dichloromethane from diisopropoxytitanium dichloride and benzyltriethylammonium borohydride in a 1:2 ratio selectively reduces aldehydes, ketones, acid chlorides, carboxylic acids, and N-Boc-protected amino acids to the corresponding alcohols in excellent yield under very mild reaction conditions (-78 to 25 degrees C).

The structural theory and physical organic chemistry

Woolley's revolutionary proposal that quantum mechanics does not sanction the concept of ''molecular structure'' - which is but only a ''metaphor'' - has fundamental implications for physical organic chemistry. On the one hand, the Uncertainty Principle limits the precision with which transition state structures may be defined; on the other, extension of the structure concept to the transition state may be unviable. Attempts to define transition states have indeed caused controversy. Consequences for molecular recognition, and a mechanistic classification, are also discussed.

First-order hyperpolarizabilities and pKa of weak organic acids in protic solvents are lineraly related

Second-order nonlinearities (beta) of five weak organic acids in protic solvents have been measured by the double-quantum Rayleigh scattering (DRS) technique. beta is found to bear a linear relationship to the pK(a) of these compounds in those solvents. A direct implication of this observation is that the DRS technique can be used to determine the pK(a) of weak organic acids in any solvent.

The principle of microscopic reversibility in organic chemistry - a critique

The principle of microscopic reversibility is one of the few generalising principles used in organic chemistry which have their roots in the fundamental laws of thermodynamics. It has, therefore, been highly popular. However, although the principle has some important uses, its general application is not without pitfalls. The principle is easy to misunderstand and to misapply: indeed, some of its formulations are semantically dubious. The principle is most dangerous when used as a charm, for it is more subtle than some of its formulations suggest. But above all, the principle may not be used for deducing or disproving the mechanism of a reaction, except when the mechanism in the reverse direction is known independently. For, such use is, perhaps, the deadliest misapplication.

Organic Additive-Mediated Synthesis of Novel Cobalt(II) Hydroxides

Electrochemical precipitation of cobalt(II) hydroxide from nitrate solutions containing organic molecules, such as glucose, fructose, lactose, glycerol, and citric acid, yields a new modification of cobalt (II) hydroxide (a = 3.09 +/- 0.03 Angstrom, c = 23.34 +/- 0.36 Angstrom) that is isostructural with cu-nickel hydroxide; precipitation in the absence of organic additives gives the stable, brucite-like, beta-CO (OH)(2). (C) 1995 Academic Press, Inc.

Reductive dimerization of organic thiocyanates to disulfides mediated by tetrathiomolybdate

An interesting reductive dimerization of organic thiocyanates assisted by benzyltriethylammonium tetrathiomolybdate, [(PhCH(2)NEt(3))(2)MoS4], 1, leads to the formation of the corresponding disulfides in high yields.

Dissociation constants of weak organic acids in protic solvents obtained from their first hyperpolarizabilities in solution

The first hyperpolarizabilities (beta) of some weak aromatic organic acids have been measured in protic solvents by the hyper-Rayleigh scattering (HRS) technique at low concentrations. The measured hyperpolarizability (beta(m)) varies between the two extreme limits: the hyperpolarizability of the acid form (beta(HA)) at the lower side and that of the basic form (beta(A-)) at the higher side. The degree of dissociation (alpha) of the acid in a solvent is related to the measured hyperpolarizability, beta(m), by the following relationship: beta(m)(2)=(1-alpha)beta(HA)(2)+alpha beta(A-)(2). The calculated beta's including solvent effects in terms of an Onsager field do not reproduce the experimentally measured hyperpolarizabilities. Other solvent-induced effects like hydrogen bonding and van der Waals interactions seem to influence the first hyperpolarizability and, thus, indirectly the extent of dissociation of these weak acids in these protic solvents.

Hydrogen-Bond-Directed Nonlinear-Optical Organic Materials - Evidence For The Control Of 2nd-Harmonic Generation Activities From The X-Ray Crystal-Structures Of The Complexes Of L-Tartaric Acid With M-Anisidine and P-Toluidine

Several substituted anilines were converted to binary salts with L-tartaric acid. Second harmonic generation (SHG) activities of these salts were determined. The crystal packing in two structures, (i) m-anisidinium-L-tartrate monohydrate (i) and (ii) p-toluidinium-L-tartrate (2), studied using X-ray diffraction demonstrates that extensive hydrogen bonding steers the components into a framework which has a direct bearing on the SHG activity

Influence of carbide particles on the dynamic recrystallization of as-cast 304 stainless steel: a study using secondary ion mass spectrometric (SIMS) analysis

The domain of dynamic recrystallization (DRX) in as-cast 304 stainless steel material occurs at higher temperatures (1250 degrees C) and lower strain rates (0.001 s(-1)) than in wrought 304 stainless steel (1100 degrees C and 0.01 s(-1)). The above result has been explained earlier on the basis of a simple theoretical DRX model involving the rate of nucleation versus rate of grain boundary migration. The present investigation is aimed at examining experimentally the influence of carbide particles on the DRX of ascast 304 using secondary ion mass spectrometric (SIMS) analysis. Isothermal compression tests at a constant true strain rate have been performed on wrought 304 and as-cast 304 materials in the temperature and strain rate ranges of 1000 to 1250 degrees C and 0.001 to 1 s(-1) respectively. The SIMS analysis carried out on the deformed samples revealed that the large carbides present in the as-cast 304 material strongly influence the DRX process. In as-cast 304 material, the presence of large carbide particles in the microstructure shifts the DRX domain to higher temperature and lower strain rate in comparison with wrought 304 material.

New open-framework phosphate and phosphite compounds of gallium

Five new open-framework compounds of gallium have been synthesized by hydrothermal methods and their structures determined by single crystal X-ray diffraction studies. The compounds, C8N4H26]Ga6F4(PO4)(6)], I, C5N3H11]Ga3F2(PO4)(3)]center dot H2O, II, C6N3H19]Ga-4(C2O4)(PO4)(4)(H2PO4)]center dot 2H(2)O, III, Ga2F3(HPO4)(PO4)]center dot 2H(3)O, IV, and C3N2H5](2)Ga-4(H2O)(3)(HPO3)(7)], V, possess three-dimensional structures. All the compounds are formed by the connectivity between the Ga polyhedra and phosphite/phosphate units. The observation of SBU-6 (I and II) and spiro-5 (IV) secondary building units (SBUs) are noteworthy. The flexibility of the formation of gallium phosphate frameworks has been established by the isolation of two related structures (I and II) from the same SBU units but different organic amines. Some of the present structures have close resemblance to the gallium phosphate phases known earlier. The compounds have been characterized by CHN analysis, powder XRD, IR, and TGA. (C) 2011 Elsevier B. V. All rights reserved.

Airborne measurements of aerosol scattering properties above the MABL over Bay of Bengal during W_ICARB - characteristics and spatial gradients

Realizing the importance of aerosol characterization and addressing its spatio-temporal heterogeneities over Bay of Bengal (BoB), campaign mode observations of aerosol parameters were carried out using simultaneous cruise, aircraft and land-based measurements during the Winter Integrated Campaign for Aerosols gases and Radiation Budget (W_ICARB). Under this, airborne measurements of total and hemispheric backscatter coefficients were made over several regions of coastal India and eastern BoB using a three wavelength integrating nephelometer. The measurements include high resolution multi-level (ML) sorties for altitude profiles and bi-level (BL) sorties for spatial gradients within and above the Marine Atmospheric Boundary Layer (MABL) over BoB. The vertical profiles of the scattering coefficients are investigated in light of the information on the vertical structure of the atmospheric stability, which was derived from the collocated GPS (Global Positioning System) aided radiosonde ascents. In general, the altitude profiles revealed that the scattering coefficient remained steady in the convectively well-mixed regions and dropped off above the MABL. This decrease was quite rapid off the Indian mainland, while it was more gradual in the eastern BoB. Investigation on horizontal gradients revealed that the scattering coefficients over northern BoB are 3 to 4 times higher compared to that of central BoB within and above the MABL. A north-south gradient in scattering coefficients is observed over Port Blair in the eastern BoB, with values decreasing from south to north, which is attributed to the similar gradient in the surface wind speed, which can be replicated in the sea salt abundance. The gradients are parameterized using best-fit analytical functions.

Studies on structural and electrical properties of barium strontium titanate thin films developed by metallo-organic decomposition

Thin films of barium strontium titanate (BST) including BaTiO3 and SrTiO3 end members were deposited using the metallo-organic decomposition (MOD) technique. Processing parameters such as nonstoichiometry, annealing temperature and time, film thickness and doping concentration were correlated with the structural and electrical properties of the films. A random polycrystalline structure was observed for all MOD films under the processing conditions in this study. The microstructures of the films showed multi-grains structure through the film thickness. A dielectric constant of 563 was observed for (Ba0.7Sr0.3)TiO3 films rapid thermal annealed at 750 degrees C for 60 s. The dielectric constant increased with annealing temperature and film thickness, while the dielectric constant could reach the bulk values for thicknesses as thin as similar to 0.3 mu m. Nonstoichiometry and doping in the films resulted in a lowering of the dielectric constant. For near-stoichiometric films, a small dielectric dispersion obeying the Curie-von Schweidler type dielectric response was observed. This behavior may be attributed to the presence of the high density of disordered grain boundaries. All MOD processed films showed trap-distributed space-charge limited conduction (SCLC) behavior with slope of similar to 7.5-10 regardless of the chemistry and processing parameter due to the presence of main boundaries through the film thickness. The grain boundaries masked the effect of donor-doping, so that all films showed distributed-trap SCLC behavior without discrete-traps. Donor-doping could significantly improve the time-dependent dielectric breakdown behavior of BST thin films, mostly likely due to the lower oxygen vacancy concentration resulted from donor-doping. From the results of charge storage density, leakage current and time-dependent dielectric breakdown behavior, BST thin films are found to be promising candidates for 64 and 256Mb ULSI DRAM applications. (C) 1997 Elsevier Science S.A.

Sub-micrometre spherical particles of TiO2, ZrO2, and PZT by nebulized spray pyrolysis of metal-organic precursors

Nebulized spray pyrolysis of metal-organic precursors in methanol solution has been employed to prepare powders of TiO2, ZrO2 and PbZr0.5Ti0.5O3 (PZT). This process ensures complete decomposition of the precursors at relatively low temperatures. The particles have been examined by scanning and transmission electron microscopy as well as X-ray diffraction. As prepared, the particles are hollow agglomerates of diameter 0.1-1.6 mu m, but after heating to higher temperatures the ultimate size of the particles comprising the agglomerates are considerably smaller (0.1 mu m or less in diameter) and crystalline.