Experimental and Theoretical Charge Density Analysis of Polymorphic Structures: The Case of Coumarin 314 Dye

Experimental charge density distributions in two known conformational polymorphs (orange and yellow) of coumarin 314 dye are analyzed based on multipole modeling of X-ray diffraction data collected at 100 K. The experimental results are compared with the charge densities derived from multipole modeling of theoretical structure factors obtained from periodic quantum calculation with density functional theory (DFT) method and B3LYP/6-31G(d,p) level of theory. The presence of disorder at the carbonyl oxygen atom of ethoxycarbonyl group in the yellow form, which was not identified earlier, is addressed here. The investigationof intermolecular interactions, based on Hirshfeld surface analysis and topological properties via quantum theory of atoms in molecule and total electrostatic interaction energies, revealed significant differences between the polymorphs. The differences of electrostatic nature in these two polymorphic forms were unveiled via construction of three-dimensional deformation electrostatic potential maps plotted over the molecular surfaces. The lattice energies evaluated from ab initio calculations on the two polymorphic forms indicate that the yellow form is likely to be the most favorable thermodynamically. The dipole moments derived from experimental and theoretical charge densities and also from Lorentz tensor approach are compared with the single-molecule dipole moments. In each case, the differences of dipole moments between the polymorphs are identified.

Accurate determination of interference in pin joints Pin-to-plate interference in experimental models of interference-fit joints is significantly overestimated by direct physical measurements, but it can be accurately determined by a simple photoelastic method

Suitable pin-to-hole interference can significantly increase the fatigue life of a pin joint. In practical design, the initial stresses due to interference are high and they are proportional to the effective interference. In experimental studies on such joints, difficulties have been experienced in estimating the interference accurately from physical measurements of pin and hole diameters. A simple photoelastic method has been developed to determine the effective interference to a high degree of accuracy. This paper presents the method and reports illustrative data from a successful application thereof.

A generalized mathematical theory and experimental verification of proportional notches

A theory and generalized synthesis procedure is advocated for the design of weir notches and orifice-notches having a base in any given shape, to a depth a, such that the discharge through it is proportional to any singular monotonically-increasing function of the depth of flow measured above a certain datum. The problem is reduced to finding an exact solution of a Volterra integral equation in Abel form. The maximization of the depth of the datum below the crest of the notch is investigated. Proof is given that for a weir notch made out of one continuous curve, and for a flow proportional to the mth power of the head, it is impossible to bring the datum lower than (2m − 1)a below the crest of the notch. A new concept of an orifice-notch, having discontinuity in the curve and a division of flow into two distinct portions, is presented. The division of flow is shown to have a beneficial effect in reducing the datum below (2m − 1)a from the crest of the weir and still maintaining the proportionality of the flow. Experimental proof with one such orifice-notch is found to have a constant coefficient of discharge of 0.625. The importance of this analysis in the design of grit chambers is emphasized.

A semi-experimental approach to plane problems in elasticity

A semi-experimental approach to solve two-dimensional problems in elasticity is given. The method has been applied to two problems, (i) a square deep beam, and (ii) a bridge pier with a sloping boundary. For the first problem sufficient analytical results are available and hence the accuracy of the method can be verified. Then the method has been extended to the second problem for which sufficient results are not available.

Experimental studies on the wear of engine components

Wear studies of engine components of high-speed diesel engines running under various operating conditions are presented. Tests were conducted under controlled conditions over long periods. The results of the various tests are discussed and attempts have been made to examine the effects of engine operating variables and the quality of the lubricating oil on the wear of engine components.

Some experimental observations on the use of activated sludge as fertilizer for fish culture

Experiments were conducted in cement cisterns to find out the effect of adding different dosages of activated sludge on fish growth and plankton production. Three dosages of sludge,viz., 62·5 gm., 125 gm. and 250 gm. per 240 litres of water were used. Fingerlings ofCyprinus carpio, Cirrhina mrigala andCatla catla responded positively,C. mrigala showing maximum growth. The results indicate that the sludge has a direct influence on increasing growth of fish and production of plankton due to the release of nutrients into the water. The increase in plankton content stops after about 30 days. When greater quantities of sludge were added in the cisterns, fish mortality took place.

Experimental evidence of the cavity theory of sorption-desorption hysteresis by a study of the effect of electric discharge on entrapped water in silica gel

With the use of the quartz fiber spring balance, sorptions and desorptions of water on silica gel at 30°C were studied and the permanent and reproducible hysteresis loop was obtained. At different points on the desorption curve forming the loop, the gel was subjected to high tension glow electric discharge. As a result of the electric discharge, the gel at any point on the desorption curve shifts to a corresponding point on the sorption curve. This is due to the release from the cavities of gel of the entrapped water held in a metastable state. The electric discharge has no effect on the gel at different points on portions of the desorption curve which coincide with the sorption curve and also on the sorption curve itself, indicating the absence of entrapped water in the gel in these regions. The results afford direct experimental evidence of the reality of the cavity theory of sorption-desorption hysteresis.

Crystalline ethane-1,2-diol does not have intra-molecular hydrogen bonding: Experimental and theoretical charge density studies

The X-ray structure and electron density distribution of ethane-1,2-diol (ethylene glycol), obtained at a resolution extending to 1.00 Å−1 in sin θ/λ (data completion = 100% at 100 K) by in situ cryocrystallization technique is reported. The diol is in the gauche (g′Gt) conformation with the crystal structure stabilised by a network of inter-molecular hydrogen bonds. In addition to the well-recognized O–H···O hydrogen bonds there is topological evidence for C–H···O inter-molecular interactions. There is no experimental electron density based topological evidence for the occurrence of an intra-molecular hydrogen bond. The O···H spacing is not, vert, similar0.45 Å greater than in the gas-phase with an O–H···O angle close to 90°, calling into question the general assumption that the gauche conformation of ethane-1,2-diol is stabilised by the intra-molecular oxygen–hydrogen interaction.

Effectiveness of a Differential Temperature Controller on a Solar Water Heating System: An Experimental Study

A differential temperature controller is incorporated in a solar water heating system to study the influence of its set points on system performance. The effectiveness of the controller set points DeltaT ON and DeltaT OFF on the pump cycling and energy collection has been studied experimentally and the results are presented in this paper.

Assessment of ultrasound modulation of near infrared light on the quantification of scattering coefficient

Purpose: To assess the effect of ultrasound modulation of near infrared (NIR) light on the quantification of scattering coefficient in tissue-mimicking biological phantoms.Methods: A unique method to estimate the phase of the modulated NIR light making use of only time averaged intensity measurements using a charge coupled device camera is used in this investigation. These experimental measurements from tissue-mimicking biological phantoms are used to estimate the differential pathlength, in turn leading to estimation of optical scattering coefficient. A Monte-Carlo model base numerical estimation of phase in lieu of ultrasound modulation is performed to verify the experimental results. Results: The results indicate that the ultrasound modulation of NIR light enhances the effective scattering coefficient. The observed effective scattering coefficient enhancement in tissue-mimicking viscoelastic phantoms increases with increasing ultrasound drive voltage. The same trend is noticed as the ultrasound modulation frequency approaches the natural vibration frequency of the phantom material. The contrast enhancement is less for the stiffer (larger storage modulus) tissue, mimicking tumor necrotic core, compared to the normal tissue. Conclusions: The ultrasound modulation of the insonified region leads to an increase in the effective number of scattering events experienced by NIR light, increasing the measured phase, causing the enhancement in the effective scattering coefficient. The ultrasound modulation of NIR light could provide better estimation of scattering coefficient. The observed local enhancement of the effective scattering coefficient, in the ultrasound focal region, is validated using both experimental measurements and Monte-Carlo simulations. (C) 2010 American Association of Physicists in Medicine. [DOI: 10.1118/1.3456441]