Role of organic fluorine in crystal engineering

The design of compounds with novel and improved physico-chemical properties as advanced functional materials with a specific application spectrum requires the knowledge about possible supramolecular packing motifs and their experimental control in crystalline lattice. Besides the structure of the individual molecule, non-covalent interactions play a significant role in the determination of molecular conformation, along with the formation of three-dimensional supramolecular architecture in a crystal as a requirement for molecular recognition processes, and the related bioactivity. Involvement of functional groups will contribute to the formation of a predefined packing motif due to their well-defined interactions. The strength and directionality of these interactions create characteristic packing motifs, which can be used for the design of supramolecular arrangements by the development of appropriate strategies for the precise control of their topology. Most relevant of these non-covalent interactions are stacking interactions and hydrogen bonds, which have been subjects of extensive study in the last two decades. In recent literature, substantial efforts have been put in by various researchers towards the understanding of interactions involving organic fluorine and the role they play in generating different packing motifs which guides assembling of molecules in the crystal lattice.

Sonochemical reaction engineering

Ultrasound has been widely used by chemists to enhance yields as well as rates of homogeneous as well as heterogeneous chemical reactions. The effect of ultrasound on the course of chemical reactions is mediated through cavitation bubbles it generates. High temperatures and pressures are attained inside the cavitating bubbles when they collapse. The extreme conditions so generated lead to the formation of reactive intermediates, e.g., free radiacls, inside the bubbles, which cause chemical reactions to occur when they enter the surrounding liquid. This is the mechanism through which ultrasound influences the path of homogeneous reactions. The cavitation bubbles collapse asymmetrically in the vicinity of solids, e.g., catalyst particles. Asymmetric collapse lead to formation of high speed microjets. The microjets can enhance transport rates, the increase surface area through pitting as well as particle fragmentation through collisions. Both can alter the rates of heterogeneous reaction rates. It however appears that these effects do not exhaust the scope of the influence of ultrasound on heterogeneous reactions. Modelling and quantitative prediction of the effect of ultrasound on chemical reactions is however at a stage of infancy as the phenomena are complex. Only a few examples of modelling exist in literature. Apart from this, reactor design and scaleup pose significant problems. Thus sonochemical reaction engineering offers large scope for research and development efforts.

Studies in crystal engineering: structure�reactivity correlations of substituted styrylcoumarins and related systems

The solid state photochemical behaviour of 7-hydroxy-4-styrylcoumarin 1 and several of its derivatives and analogues has been investigated. All the compounds with the exception of 7-methoxy-4-styrylcoumarin 2 are photolabile and yield anti-HT dimers. It has been observed that chloro substitution in the systems studied does not lead to the expected beta-packing mode. The photobehaviour of 1 and 2 has been correlated with their crystal structures. Reasons for alpha-packing have been examined. The systematics in the arrangement of the carbonyl group and phenyl group of the close neighbours in the crystals of 1, 2 and a few other cases are presented.

Reflections on the Hydrogen Bond in Crystal Engineering

Comments on aspects of the new definition of the hydrogen bond specific to crystal engineering are given.

Active vibration suppression of beams with discrete actuators using optimal dynamic inversion

Most of the structural elements like beams, cables etc. are flexible and should be modeled as distributed parameter systems (DPS) to represent the reality better. For large structures, the usual approach of 'modal representation' is not an accurate representation. Moreover, for excessive vibrations (possibly due to strong wind, earthquake etc.), external power source (controller) is needed to suppress it, as the natural damping of these structures is usually small. In this paper, we propose to use a recently developed optimal dynamic inversion technique to design a set of discrete controllers for this purpose. We assume that the control force to the structure is applied through finite number of actuators, which are located at predefined locations in the spatial domain. The method used in this paper determines control forces directly from the partial differential equation (PDE) model of the system. The formulation has better practical significance, both because it leads to a closed form solution of the controller (hence avoids computational issues) as well as because a set of discrete actuators along the spatial domain can be implemented with relative ease (as compared to a continuous actuator)

Crystal Structure Engineering by Fine-Tuning the Surface Energy: The Case of CdE (E = S/Se) Nanocrystals

We prove that CdS nanocrystals can be thermodynamically stabilized in both wurtzite and zinc-blende crystallographic phases at will, just by the proper choice of the capping ligand. As a striking demonstration of this, the largest CdS nanocrystals (similar to 15 nm diameter) ever formed with the zinc-blende structure have been synthesized at a high reaction temperature of 310 degrees C, in contrast to previous reports suggesting the formation of zinc-blende CdS only in the small size limit (< 4.5 nm) or at a lower reaction temperature (<= 240 degrees C). Theoretical analysis establishes that the binding energy of trioctylphosphine molecules on the (001) surface of zinc-blende CdS is significantly larger than that for any of the wurtzite planes. Consequently, trioctylphosphine as a capping agent stabilizes the zinc-blende phase via influencing the surface energy that plays an important role in the overall energetics of a nanocrystal. Besides achieving giant zinc-blende CdS nanocrystals, this new understanding allows us to prepare CdSe and CdSe/CdS core/shell nanocrystals in the zinc-blende structure.

Critical earthquake input power spectral density function models for engineering structures

The problem of determining optimal power spectral density models for earthquake excitation which satisfy constraints on total average power, zero crossing rate and which produce the highest response variance in a given linear system is considered. The solution to this problem is obtained using linear programming methods. The resulting solutions are shown to display a highly deterministic structure and, therefore, fail to capture the stochastic nature of the input. A modification to the definition of critical excitation is proposed which takes into account the entropy rate as a measure of uncertainty in the earthquake loads. The resulting problem is solved using calculus of variations and also within linear programming framework. Illustrative examples on specifying seismic inputs for a nuclear power plant and a tall earth dam are considered and the resulting solutions are shown to be realistic.

Origin of a trend in ECMWF wind analysis and its objective removal

The suitability of the European Centre for Medium Range Weather Forecasting (ECMWF) operational wind analysis for the period 1980-1991 for studying interannual variability is examined. The changes in the model and the analysis procedure are shown to give rise to a systematic and significant trend in the large scale circulation features. A new method of removing the systematic errors at all levels is presented using multivariate EOF analysis. Objectively detrended analysis of the three-dimensional wind field agrees well with independent Florida State University (FSU) wind analysis at the surface. It is shown that the interannual variations in the detrended surface analysis agree well in amplitude as well as spatial patterns with those of the FSU analysis. Therefore, the detrended analyses at other levels as well are expected to be useful for studies of variability and predictability at interannual time scales. It is demonstrated that this trend in the wind field is due to the shift in the climatologies from the period 1980-1985 to the period 1986-1991.

Review of hypersonic research investigations in IISc shock tunnel (HST1)

Real gas effects dominate the hypersonic flow fields encountered by modem day hypersonic space vehicles. Measurement of aerodynamic data for the design applications of such aerospace vehicles calls for special kinds of wind tunnels capable of faithfully simulating real gas effects. A shock tunnel is an established facility commonly used along with special instrumentation for acquiring the data for this purpose within a short time period. The hypersonic shock tunnel (HST1), established at the Indian Institute of Science (IISc) in the early 1970s, has been extensively used to measure the aerodynamic data of various bodies of interest at hypersonic Mach numbers in the range 4 to 13. Details of some important measurements made during the period 1975-1995 along with the performance capabilities of the HST1 are presented in this review. In view of the re-emergence of interest in hypersonics across the globe in recent times, the present review highlights the Suitability of the hypersonic shock tunnel at the IISc for future space application studies in India.

Studies in crystal engineering: Effect of fluorine substitution in crystal packing and topological photodimerization of styryl coumarins in the solid state

Styryl coumarins generally yield centrosymmetric (alpha-mode, anti-HT) photodimers when subjected to irradiation in the solid state, However, the substitution of fluorine dramatically alters the packing mode and steers the molecules 4-(4-fluorostyryl)coumarin 1 and 4-(2-fluorostyryl)coumarin 2 to form a stereospecific photodimer, beta-mode, syn-HH across the styrenic double bond (yield 78-85%). The stereochemistry of the photodimer 2a has been established by X-ray crystallography. There is no evidence for the presence of C-H ... F interactions. The true nature of the weak atom-atom interactions called into play when fluorine is substituted is not clear, It is observed that the fluoro substituted compounds have greater crystal density than the corresponding unsubstituted ones.

Some Basic Aspects of Reaction Engineering of Precipitation Processes

Analysis of precipitation reactions is extremely important in the technology of production of fine particles from the liquid phase. The control of composition and particle size in precipitation processes requires careful analysis of the several reactions that comprise the precipitation system. Since precipitation systems involve several, rapid ionic dissociation reactions among other slower ones, the faster reactions may be assumed to be nearly at equilibrium. However, the elimination of species, and the consequent reduction of the system of equations, is an aspect of analysis fraught with the possibility of subtle errors related to the violation of conservation principles. This paper shows how such errors may be avoided systematically by relying on the methods of linear algebra. Applications are demonstrated by analyzing the reactions leading to the precipitation of calcium carbonate in a stirred tank reactor as well as in a single emulsion drop. Sample calculations show that supersaturation dynamics can assume forms that can lead to subsequent dissolution of particles that have once been precipitated.

Growth and development of Thiobacillus ferrooxidans for engineering applications

A bioprocessing approach for the extraction of base, nuclear and precious metals from refractory and lean grade ores has been reviewed in this paper. Characteristic morphological features of Thiobacillus ferrooxidans, the organism which has been extensively used for biooxidation of sulphide ores have been discussed. Mechanisms of chemoautotrophy and mineral oxidation have been illustrated. The current engineering applications of this microorganism have also been brought out. Various methods for accelerating the growth of Thiobacillus ferrooxidans for faster biooxidation and genetic manipulation for development of desired strains have been outlined.

Studies in crystal engineering: Crystal packing, topological photodimerization and structure-reactivity correlations in fluoro-substituted styrylcoumarins

In continuation of our studies on the influence of fluoro substitution on the solid state photobehaviour and packing pattern of styrylcoumarins, the results obtained for 4-(3-fluorostyryl)coumarin 1, 4-styryl-6-fluorocoumarin 2 and 4-styryl-7-fluorocoumarin 3 are presented. The configuration of the dimers was established on the basis of crystal packing of 1 and 2 (alpha-packed). A rationale for the significantly lower dimer yield in the crystal for 2 is proposed. In the observed centrosymmetric arrangement of the reactants the C=O ...pi (phenyl) contacts seem to provide additional attractive interactions. C-H ... O and C-H ... F hydrogen bonding seems to provide stability in these structures.

Studies in crystal engineering: Steering ability of fluorine in styrylcoumarins

In continuation of our studies on crystal engineering using fluorine as a steering group, the photobehaviour of di and tri fluoro 4-styrylcoumarins has been examined. It is found that out of the five derivatives, four crystallize into P-packing mode producing syn-HH photodimer upon irradiation whereas the parent hydrocarbon produces an anti K-T dimer. The packing features of the photolabile crystals of 4-(4-fluorostyryl)-6-fluorocoumarin (1), 4-(2,6-difluorostyryl) 6-fluorocoumarin (2) and the photodimer (3a) of 4-(2,6-fluorostyryl)-7-fluorocoumarin (3) have been determined by single crystal X-ray diffraction studies. The stereochemistry of the photodimer of 4-(2-fluorostyryl)-6-fluorocoumarin (4) is deduced based on preliminary X-ray crystallographic data. However, 4-(2,6-difluorostyryl) coumarin (5) is photoinert. The remarkable steering ability of fluorine is established with the molecular packing in the crystal lattice leading to the formation of syn H-H dimer in the above four examples. (C) 1999 Elsevier Science Ltd. All rights reserved.