Orientational melting and reorientational motion in a cubane molecular crystal: A molecular simulation study

Detailed molecular simulations are carried out to investigate the effect of temperature on orientational order in cubane molecular crystal. We report a transition from an orientationally ordered to an orientationally disordered plastic crystalline phase in the temperature range 425-450 K. This is similar to the experimentally reported transition at 395 K. The nature of this transition is first order and is associated with a 4.8% increase in unit Cell volume that is comparable to the experimentally reported unit cell volume change of 5.4% (Phys. Rev. Lett. 1997, 78, 4938). An orientational order parameter, eta(T), has been defined in terms of average angle of libration of a molecular 3-fold axis and the orientational melting has been characterized by using eta(T). The orientational melting is associated with an anomaly in specific heat at constant pressure (C-p) and compressibility (kappa). The enthalpy of transition and entropy of transition associated with this orientational melting are 20.8 J mol(-1) and 0.046 J mol(-1) K-1, respectively. The structure of crystalline as well as plastic crystalline phases is characterized by using various radial distribution functions and orientational distribution functions. The coefficient of thermal expansion of the plastic crystalline phase is more than twice that of the crystalline phase.

Studies in bubble formation — III

Bubble formation from single horizontal orifices submerged in Newtonian liquids has been investigated for such chamber volumes that both the pressure inside the chamber and flow rate into the bubble are time dependent. The data collected show that under these conditions the bubble volume decreases exponentially with increase in orifice submergence. The equations for the generalized two stage model of bubble formation, taking the variation of gas flow rate with time into account, have been derived. These equations reduce to the cases of constant gas flow rate and constant pressure when adequate constraints are imposed. The results obtained under intermediate conditions have been quantitatively explained on the basis of these equations.

Mass spectrometry and n-in-one analytics in early drug discovery: Combinatorial chemistry libraries, lipophilicity and absorption screening

This thesis describes current and past n-in-one methods and presents three early experimental studies using mass spectrometry and the triple quadrupole instrument on the application of n-in-one in drug discovery. N-in-one strategy pools and mix samples in drug discovery prior to measurement or analysis. This allows the most promising compounds to be rapidly identified and then analysed. Nowadays properties of drugs are characterised earlier and in parallel with pharmacological efficacy. Studies presented here use in vitro methods as caco-2 cells and immobilized artificial membrane chromatography for drug absorption and lipophilicity measurements. The high sensitivity and selectivity of liquid chromatography mass spectrometry are especially important for new analytical methods using n-in-one. In the first study, the fragmentation patterns of ten nitrophenoxy benzoate compounds, serial homology, were characterised and the presence of the compounds was determined in a combinatorial library. The influence of one or two nitro substituents and the alkyl chain length of methyl to pentyl on collision-induced fragmentation was studied, and interesting structurefragmentation relationships were detected. Two nitro group compounds increased fragmentation compared to one nitro group, whereas less fragmentation was noted in molecules with a longer alkyl chain. The most abundant product ions were nitrophenoxy ions, which were also tested in the precursor ion screening of the combinatorial library. In the second study, the immobilized artificial membrane chromatographic method was transferred from ultraviolet detection to mass spectrometric analysis and a new method was developed. Mass spectra were scanned and the chromatographic retention of compounds was analysed using extract ion chromatograms. When changing detectors and buffers and including n-in-one in the method, the results showed good correlation. Finally, the results demonstrated that mass spectrometric detection with gradient elution can provide a rapid and convenient n-in-one method for ranking the lipophilic properties of several structurally diverse compounds simultaneously. In the final study, a new method was developed for caco-2 samples. Compounds were separated by liquid chromatography and quantified by selected reaction monitoring using mass spectrometry. This method was used for caco-2 samples, where absorption of ten chemically and physiologically different compounds was screened using both single and nin- one approaches. These three studies used mass spectrometry for compound identification, method transfer and quantitation in the area of mixture analysis. Different mass spectrometric scanning modes for the triple quadrupole instrument were used in each method. Early drug discovery with n-in-one is area where mass spectrometric analysis, its possibilities and proper use, is especially important.

On the ignition and extinction problems in forced convection systems

In this paper the problem of ignition and extinction has been formulated for the flow of a compressible fluid with Prandtl and Schmidt numbers taken as unity. In particular, the problems of (i) a jet impinging on a wall of combustible material and (ii) the opposed jet diffusion flame have been studied. In the wall jet case, three approximations in the momentum equation namely, (i) potential flow, (ii) viscous flow, (ii) viscous incompressible with k = 1 and (iii) Lees' approximation (taking pressure gradient terms zero) are studied. It is shown that the predictions of the mass flow rates at extinction are not very sensitive to the approximations made in the momentum equation. The effects of varying the wall temperature in the case (i) and the jet temperature in the case (ii) on the extinction speeds have been studied. The effects of varying the activation energy and the free stream oxidant concentration in case (ii), have also been investigated.

Large-scale structures in turbulent and reverse-transitional sink flow boundary layers

Aspects of large-scale organized structures in sink flow turbulent and reverse-transitional boundary layers are studied experimentally using hot-wire anemometry. Each of the present sink flow boundary layers is in a state of 'perfect equilibrium' or 'exact self-preservation' in the sense of Townsend (The Structure of Turbulent Shear Flow, 1st and 2nd edns, 1956, 1976, Cambridge University Press) and Rotta (Progr. Aeronaut. Sci., vol. 2, 1962, pp. 1-220) and conforms to the notion of 'pure wall-flow' (Coles, J. Aerosp. Sci., vol. 24, 1957, pp. 495-506), at least for the turbulent cases. It is found that the characteristic inclination angle of the structure undergoes a systematic decrease with the increase in strength of the streamwise favourable pressure gradient. Detectable wall-normal extent of the structure is found to be typically half of the boundary layer thickness. Streamwise extent of the structure shows marked increase as the favourable pressure gradient is made progressively severe. Proposals for the typical eddy forms in sink flow turbulent and reverse-transitional flows are presented, and the possibility of structural self-organization (i.e. individual hairpin vortices forming streamwise coherent hairpin packets) in these flows is also discussed. It is further indicated that these structural ideas may be used to explain, from a structural viewpoint, the phenomenon of soft relaminarization or reverse transition of turbulent boundary layers when subjected to strong streamwise favourable pressure gradients. Taylor's 'frozen turbulence' hypothesis is experimentally shown to be valid for flows in the present study even though large streamwise accelerations are involved, the flow being even reverse transitional in some cases. Possible conditions, which are required to be satisfied for the safe use of Taylor's hypothesis in pressure-gradient-driven flows, are also outlined. Measured convection velocities are found to be fairly close to the local mean velocities (typically 90% or more) suggesting that the structure gets convected downstream almost along with the mean flow.

On the bursting criterion for laminar separation bubbles

Traditionally, laminar separation bubbles have been characterised as being 'long' or 'short' on the basis of a two parameter 'bursting' criterion involving a pressure gradient parameter and Reynolds Number at separation. In the present work we suggest a refined bursting criterion, which takes into account not just the length of the bubble but also the maximum height of the bubble, thereby shedding some light on the less understood phenomenon of 'bursting' in laminar separation bubbles.

On the momentum balance in linear-combination models for the transition zone

The momentum balance of the linear-combination integral model for the transition zone is investigated for constant pressure flows. The imbalance is found to be small enough to be negligible for all practical purposes. [S0889-504X(00)00703-0].

A simple technique for approximate solutions of the Falkner-Skan equation

A simple, sufficiently accurate and efficient method for approximate solutions of the Falkner-Skan equation is proposed here for a wide range of the pressure gradient parameter. The proposed approximate solutions are obtained utilising a known solution of another differential equation.

Novel kinetic scheme for the ammonium perchlorate gas phase

A novel gas-phase kinetic scheme for ammonium perchlorate (AP) deflagration involving 22 reactions among 18 species is developed. The kinetic scheme is based on a study of the effect of initial conditions on the solution of the differential equations of adiabatic constant-pressure combustion kinetics. The existence of condensed-phase reaction products providesalternate pathways for the consumption of NH3 and HCIOl produced by gas-phase dissociation of AP. Theoretically obtained temperature-time profiles of the novel scheme do not change when the conventional reaction pathways are included, indicatingthat the novel scheme is a substantially faster rate process. The new scheme does not involve the species CIO, which has long been considered a critical component of the AP gas phase and which is included in the conventional reaction pathways.The new scheme develops faster overall reaction rates, steeper temperature-time profiles, and in a deflagration model will result in higher heat-transfer rates from gas phase to the condensed phase.

Nonsimilar boundary layers for non-Darcy mixed convection flow about a horizontal surface in a saturated porous medium

The nonsimilar non-Darcy mixed convection flow about a heated horizontal surface in a saturated porous medium has been studied when the surface temperature is a power function of distance (Tw = T∞ ± Axλ). The analysis is performed for the cases of parallel and stagnation flows with favourable induced pressure gradient. The partial differential equations governing the flow have been solved numerically using the Keller box method. The heat transfer is enhanced due to the buoyancy parameter and wall temperature, but the non-Darcy parameter reduces it. For non-Darcy flow, the similarity solution exists only for the case of parallel flow.

Integral method for the calculation of incompressible two-dimensional transitional boundary layers

The method proposed here considers the mean flow in the transition zone as a linear combination of the laminar and turbulent boundary layer in proportions determined by the transitional intermittency, the component flows being calculated by approximate integral methods. The intermittency distribution adopted takes into account the possibility of subtransitions within the zone in the presence of strong pressure gradients. A new nondimensional spot formation rate, whose value depends on the pressure gradient, is utilized to estimate the extent of the transition zone. Onset location is determined by a correlation that takes into account freestream turbulence and facility-specific residual disturbances in test data. Extensive comparisons with available experimental results in strong pressure gradients show that the proposed method performs at least as well as differential models, in many cases better, and is always faster.

Asukkaan Helsinki? : Tapaustutkimus vuorovaikutteisuudesta kaupunkisuunnittelussa

This study examines the interaction between inhabitants and urban planning. In addition to traditional methods of participation there can be seen an increasing need to find new channels and means to influence on one´s environment. Hearing of inhabitants during planning is hoped to decrease the amount of claims and this way to speed up the planning process. Discussion that emphasizes competitiveness and innovativeness in planning has brought out the role of inhabitants as selective consumers and end users. This extension of civil perspective completes the thought of participation in city planning and adds the pressure on developing the interaction and user orientation. The aim of the study is to point out the present situation of inhabitant´s participation and influencing in Helsinki. Helsinki City Planning Department opened a new information and exhibiotion hall called Laituri in 2008. Laituri provides the latest information about planning projects in Helsinki and temporary exhibitions as well as it operates as communication channel and information point for the department. In this study Laituri is examined as a case study of interaction between citizen and planner. The study is divided into two principal themes. The aim is to research action and interactivity at Laituri from the inhabitants´and planners´point of view. The qualitative study has inquiries, interview surveys and observation as research methods. Empiricial data of the study consists of three parts which complement each other: Laituri operational reseach, inquiry directed to the members of Laituri team and interviews of three experts. The aim is to find answers to questions like, does Laituri reach the citizens and will the opportunities to participate improve along Laituri. The study examines also how the local knowledge of inhabitants will come across to planners and further to planning. The study combines discussions of inhabitants´ influencing in Finnish society and science community. Cornerstones of the study are inhabitant participation, interaction and local knowledge in urban planning. The theory behind the study is communicative planning theory. In addition the theory consists of key concepts. The study introduces a concept of Inhabitant´s Helsinki, which reflects the inhabitant as customer-citizen who is an active product developer in participative urban planning. According to the research results the experts of Laituri and majority of inhabitants in Helsinki experience that the inhabitant´s possibilities to participate will improve along Laituri. However half of the citizens in Helsinki believe that local knowledge and ideas will only have minor impact on the final plan. According to city dwellers the present practise used by Helsinki City Planning Department supports only partially adequate interaction. The experts of Laituri experience that the role of Laituri is first of all forum of communication and discussion channel instead of effective local data collector. Based on the results the study introduces a model of inhabitant´s participation field. According to the model Laituri can be seen as phenomenom in Helsinki urban planning which has the elements of network municipality. The planner is more like diplomatic trend-setter and visionary. The inhabitant of Helsinki is an expert in city living and participative producer of local knowledge. Participation methods are increasingly segmented and tailored in every plan and project. The study argues that Inhabitant´s Helsinki is a pluralistic milieu in constant pressure for change. Therefore reaching the everyday life experiencies of inhabintants should be at higher degree in Helsinki City Planning Department´s operations.

Orientational glassy phases of C60 and neopentane. A Monte Carlo study

Based on an isothermal, isobaric simulation the structure and properties of the plastic crystalline phases of C60 and neopentane have been examined. Instantaneous cooling of the plastic crystalline phases of both C60 and neopentane leads to orientational glassy phases. These are accompanied by significant slowing down of reorientational motion. Constant pressure quench experiments on C60 yield a glass transition temperature of around 80 K.

Pulsatile flow of a viscous fluid in elliptical pipe of variable cross-section

The pulsatile flow of an incompressible viscous fluid in an elliptical pipe of slowly varying cross-section is considered. Asymptotic series solutions for the velocity distribution and pressure gradient are obtained in terms of Mathieu functions for a low Reynold number flow in which the volume flux is prescribed. An expression for shear stress on the boundary is derived. The physically significant quantities governing the flow are computed numerically and analysed for different types of constrictions. The effect of eccentricity and Womerslay parameter on the flow is discussed.

Non-uniform slot injection (suction) or wall enthalpy into a steady nonsimilar compressible laminar boundary layer

Steady two-dimensional and axisymmetric compressible nonsimilar laminar boundary-layer flows with non-uniform slot injection (or suction) and non-uniform wall enthalpy have been studied from the starting point of the streamwise co-ordinate to the exact point of separation. The effect of different free stream Mach number has also been considered. The finite discontinuities arising at the leading and trailing edges of the slot for the uniform slot injection (suction) or wall enthalpy are removed by choosing appropriate non-uniform slot injection (suction) or wall enthalpy. The difficulties arising at the starting point of the streamwise co-ordinate, at the edges of the slot and at the point of separation are overcome by applying the method of quasilinear implicit finite difference scheme with an appropriate selection of finer step size along the streamwise direction. It is observed that the non-uniform slot injection moves the point of separation downstream but the non-uniform slot suction has the reverse effect. The increase of Mach number shifts the point of separation upstream due to the adverse pressure gradient. The increase of total enthalpy at the wall causes the separation to occur earlier while cooling delays it. The non-uniform total enthalpy at the wall (i.e., the cooling or heating of the wall in a slot) along the streamwise co-ordinate has very little effect on the skin friction and thus on the point of separation.