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A Study of Supramolecular Gels and Self Assembly of Novel Bile Acid Conjugates

Electronic Theses of Indian Institute of Science

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Title A Study of Supramolecular Gels and Self Assembly of Novel Bile Acid Conjugates
 
Creator Ramesh, K
 
Subject Supramolecular Gels
Novel Bile Acid Conjugates
Supramolecular Chemistry
Bile Acid Conjugates - Self Assembly
Functional Supramolecular Gels
Responsive Supramolecular Gels
Organogels
Lanthanide Cholate Gels
Bile Acid Click Conjugates
Bile Acid Derivatives
Organogel Matrix
Bile Acid Anthracece Conjugates
Metallogels
Hybrid Gels
Deoxycholate Gel Matrix
Lanthanide(III)‐Cholate Gels
Organic Chemistry
 
Description Chapter 1: Functional and Responsive Supramolecular Gels
In this chapter ‘supramolecular gels’ derived from small organic molecules with molecular mass of typically less than 2000 daltons are discussed. Representative examples of various low molecular weight gelators based on their natural availability and also divergent functionalities are mentioned (Scheme 1).
Scheme 1
Advances in the recent years have been very rapid in the field of supramolecular chemistry of gels giving rise to ‘Tunable responsive gels’. Control of the gel property in a reversible fashion has been the highlight of responsive gels. A few of the gels which are responsive towards various stimuli such as pH, photoirradiation, cations, anions, neutral species have been discussed.
Advances and scope of supramolecular gels in various applications have also been mentioned in detail with respective examples. Utilities of supramolecular gels in synthesis of nanostructures, in biology and medicine, enzyme recognition, catalysis etc are discussed. (Scheme 2).
Chapter 2: Charge transfer triggered organogels of bis(bile acid)anthracene conjugates and 2,4.7-trinitrofluorenone.
In this chapter the study involves the synthesis of a special class of anthracene based steroidal derivatives. The appending of two amphiphilic bile acid units imparts a unique hydrophobic/ hydrophilic balance on the chromophore. The 2,3-didecyloxyanthracene (DDOA) was reported to be a gelator of various organic solvents but none of the three bile acid derivatives of anthracene synthesized was a gelator on its own. It was also observed that dialkoxy (propyl, heptyl, decyl) derivatives of anthracene formed strong charge-transfer gels in the presence of 2,4,7-trinitrofluorenone (TNF). The addition of electron deficient TNF to the steroidal derivatives of anthracene resulted in the gelation of some specific organic solvents. The driving force behind the gel formation resulted from the charge-transfer (CT) interaction between the electron rich anthracene and electron deficient fluorenone.
Figure 1. Chemical structures of 2,3-bis(bile acid)anthracenes and TNF (centre), a scanning electronic microscopy image of xerogels prepared from bis(deoxycholyl)anthracene and TNF (left) and a photograph of the gel of bis(deoxycholyl)anthracene and TNF in n-octanol.
Thermochromic property (during sol to gel phase transition), absorption and variable temperature fluorescence measurements supported CT interaction. Thermal stability studies and dynamic rheology experiments confirmed that CT gels were thermally most stable and mechanically stronger with equi-molar amounts of the two components. Stiffness values obtained from rheological experiments also suggested that the gels were viscoelastic solids.
Chapter 3(A): Tb(III) sensitization in an organogel matrix: Selective luminescence quenching by an aromatic nitro derivative
In this chapter the discovery of metallo organogel formation by mixing methanolic solutions of Tb(OAc)3 and sodium deoxycholate (NaDCh) has been explored. Sensitization of Tb3+ was observed by doping micromolar quantities of 2,3-dihydroxynaphthalene (DHN). Mechanical properties of Tb3+-DCh gels were investigated by rheology at three different ratios of Tb3+ and DCh. It was observed that increasing in the Tb3+ to DCh ratio increased the mechanical property of the gels. Time delayed emission spectra were recorded with increasing concentration of DHN and luminescence increase was noticed in a linear fashion. Importance of gel matrix was demonstrated by measuring the Tb3+ luminescence at fixed concentration (5 mM) with/without DHN in the solution and gel media.
Figure 2:: Schematic representation of Tb3+ sensitization by DHN. Photograph (right)) of the Tb3++-DCh (5/15 mM) gels with (a) 50 µM DHHN (b) No DHHN under UVV (365 nm).
Sensitization by an electron rich chromophore created interest in us to dope relatively electron deficient compounds into the gel matrix for possible quenching off Tb3+-luminescence. Among the electron deficient analytes screened included 1,5-difluro-2,4-diinitrobenzenne (DFDNB)), 2,4 dinitrophenol (DNPPh), p-nitrobenzaldehydde (p-NB), 2,4,6-trinitrootoluene (TTNT) and 22,4,7¬trinitrofluuorenone (TTNF). Microscopy studies such as AFM, TEMM and SEMM revealed highly entangled fibrous network in the morphology of Tb3+--DCh xerogel. Solid state luminescence experiments suggested that sensiitization was observed in the xerogels and extent of sensitization was comparable to that of the gel state. Xerogel soaking studies inferred the strong adherence of the DHNN to the gel fibres.
Chapter 3(B): Anion dependent structural, morphological and mechanical features of Ln(III)-Cholate gels
In this chapter the counter anion influence on various aspects of hydrogels has been discussed. It has been reported from our laboratory that mixing of aqueous solutions of sodium cholate (15 mM) and various lanthanide acetates (5 mM) followed by sonication resulted in either transparent or transluscent gels. Unsurprisingly we found that aqueous solutions of lanthanide nitrates and lanthanide chlorides also formed hydrogels upon mixing with sodium cholate (Figure 33). Dried films of Tb3++-cholate and Eu3+-cholate gels prepared from their respective nitrate salts displayed birefringent structures under polarizing optical microscopy (POM). But no significant textures of any type were observed in the case of gels prepared from either chloride or acetate salts.
Figure 3:: Photographs of the hydrogels prepared by mixing of aqueous solutions of various salts Tb33+ and Eu3+ with sodium cholate solutions. Scanning electron microscopic images exhibited fibrous structures for all the xerogels in the morphology. Atomic force microscopy and transmission electron microscopy measurements revealed helical morphology for xerogels prepared from nitrate salts where as flat tape-like cross linkage was observed for chloride or acetate based xerogels. Anion effect on mechanical properties was significant in the sense that gels prepared from acetate salts displayed highest mechanical strength followed by nitrate based gels which were stronger than that of chloride based gels. Titration of sodium cholate solution with various lanthanide salt solutions gave the direct evidence of thee pH variation as a function of the anions.
Figure 4: TEM images of xerogels prepared from gels of nitrate salts of Tb3+ (left) and Eu3+ (right)
Chapter 4: Design, synthesis a nd study of bile acid â€~click’ conjugates of perylene bisimides (PBIs) and naphthalene bisimides (NBIs)
In this chapter the synthesis of novel bile acid derivatives of perylene and naphthalene bisimides is discussed. The â€~click’ chemistry procedure was used to link bile acid groups on to the chromophores. Azide derivatives of PBIs and NBIs were prepared inn 3 step methods which were coupled to propargyl esters of bile acids by following standard â€~click chemistry’ protocols to achieve the target molecules (Scheme 3).
Scheme 3
The studies conducted mainly focused on Cholic acid (CA) conjugates of PBIs and NBIs. Steady state absorption and emission studies of CA conjugates were performed in 10% MeOH/DCM system. POM and fluorescence images showed red emissive aggregates in case of PBI films. TEM measurements revealed uniform aggregate sizes for both the films of PBI(CA)2 and NBI(CA)2. SEM and AFM (Fig 5) studies exhibited spherical aggregates of diameter around 100-200 nm for PBI(CA)2 films where as aggregates of diameter around 500-700 nm were observed for NBI(CA)2 films.
Figure 5: AFM images and their corresponding height profiles of PBI films (left) and NBI films (right)Maitra, Uday2018-04-02T14:56:35Z2018-04-02T14:56:35Z2018-04-022013Thesishttp://etd.iisc.ernet.in/2005/3307http://etd.ncsi.iisc.ernet.in/abstracts/4169/G25671-Abs.pdfen_USG25671
oai:etd.iisc.ernet.in:2005/33082018-04-02T15:01:27Zhdl_2005_34Pragmatic Design of Compliant Mechanisms using Selection MapsHegde, SudarshanMachine EngineeringComplaint MechanismsSelection Maps - Compliant MechanismsSpring-Lever ModelsSpring-Mass-Lever ModelsCompliant Mechanisms - DesignFeasible Stiffness MapsFeasible Inertia MapsGraphical User InterfaceGraphical User Interface (GUI) based DesignMechanical EngineeringA pragmatic method for designing compliant mechanisms is developed in this thesis, by selecting among existing mechanisms one that may be modified as required. This method complements existing techniques by answering questions of the existence and multiplicity of solutions for the given specifications of a practical problem. The premise for the method is a 2D map that juxta- poses the problem-specifications and the characteristics of compliant mechanisms in a database. The selection of the most suitable mechanisms is similar to Ashby's method of material selection. In our method, stuffiness, inertia, and the inherent kinematic characteristics of compliant mechanisms are analogous to material properties in Ashby's method. These characteristics capture the lumped behavior of compliant mechanisms in static and dynamic situations using spring-lever (SL) and spring-mass-lever (SML) models. The work includes the development of computation- ally efficient methods to compute the SL and SML model characteristics of single-input and single-output compliant mechanisms. Also developed in this work is a method to determine a feasible map by solving the governing equations of equilibrium and several inequalities pertaining to problem- specifications. The map helps not only in assessing the feasibility of the specifications but also in re-designing the mechanisms in predetermined ways to nd multiple solutions, all of which account for practical considerations. The method pays due attention to the overall size, strength considerations, manufacturability, and choice of material. It also enables minimal alterations of the problem-specifications when the user prefers a particular mechanism in the database. All these features are implemented in a web-based Java program with a graphical user interface that can be accessed at http://www.mecheng.iisc.ernet.in/ m2d2/CM design. Six case- studies that include micro machined inertial sensors, miniature valve mechanisms, ultra-sensitive force sensors, etc., are documented in detail to demonstrate the usefulness of the method in practice.Ananthasuresh, G K2018-04-02T15:01:27Z2018-04-02T15:01:27Z2018-04-022013Thesishttp://etd.iisc.ernet.in/2005/3308http://etd.ncsi.iisc.ernet.in/abstracts/4170/G25674-Abs.pdfen_USG25974
oai:etd.iisc.ernet.in:2005/33092018-04-02T15:27:41Zhdl_2005_27Optimal Trajectory Planning for Fixed-Wing Miniature Air VehiclesHota, SikhaAerodynamicsAircraft MiniatureFlight DynamicsMiniature Air Vehicles - Optimal Path Planning2D Planes - Path Convergence3D Space - Path ConvergenceAir Vehicles - Optimal Path ConvergenceMiniature Air VehiclesWaypoints (Miniature Air Vehicles)Dubins Vehicle FlyingUnmanned Aerial Vehicle3D Space - Rectilinear Path3D Optimal Path PlanningPontryagin's Maximum PrincipleAeronauticsApplications such as urban surveillance, search and rescue, agricultural applications, military applications, etc., require miniature air vehicles (MAVs) to fly for a long time. But they have restricted flight duration due to their dependence on battery life, which necessitates optimal path planning. The generated optimal path should obey the curvature limits prescribed by the minimum turn radius/ maximum turn rate of the MAV. Further, in a dynamically changing environment, the final configuration that the MAV has to achieve may change en route, which demands the path to be replanned by an airborne processor in real-time. As MAVs are small in size and light in weight, wind has a very significant effect on the flight of MAVs and the computation of the minimum-time path in the presence of wind plays an important role. The thesis develops feasible trajectory generation algorithms which are fast, efficient, optimal and implementable in an onboard computer for rectilinear and circular path convergence problems and waypoint following problems both in the absence and in the presence of wind.
The first part of the thesis addresses the problem of computation of optimal trajectories when MAVs fly on a two-dimensional (2D) plane maintaining a constant altitude. The shortest path is computed for MAVs from a given initial position and orientation to a given final path with a specified direction as required for a given mission. Unlike the classical Dubins problem where the shortest path was computed between two given configurations (position and orientation), the final point in this case is not specified. However, the final path, which can either be a rectilinear path or a circular path, and the direction to which the MAV should converge, is specified. The time-optimal path of MAVs is developed in the presence of wind mainly using the geometric approach although a few important properties are also obtained using optimal control theory, specifically, Pontryagin’s minimum principle (which provides only the necessary condition for optimality) for control-constrained systems. The complete optima l solution to this problem in all its generality is a major contribution of this thesis as existing methods in the literature that address this problem are either not optimal or do not give a complete solution. Further, the time-optimal path for specified initial and final configurations is generated in reasonably short time without computing all the path lengths of possible candidate paths, which is the method that exists in the literature for similar problems. Simulation results illustrate path generation for various cases, including the presence of steady and time-varying wind.
Another problem in MAV path planning in 2D addressed in this thesis computes an extremal path that transitions between two consecutive waypoint segments (obtained by joining two way points in sequence) in a time-optimal fashion. This designed trajectory, named as γ-trajectory, is also used to track the maximum portion of waypoint segments in minimum time and the shortest distance between this trajectory and the associated waypoint can be set to a desired value. Another optimal path, called the loop trajectory, that goes through the way points as well as through the entire waypoint segments, is also proposed. Subsequently, the thesis proposes algorithms to generate trajectories in the presence of steady wind and compares these with the optimal trajectory generated using nonlinear programming based multiple shooting method to show that the generated paths are optimal in most cases.
In three-dimensional (3D) space, if the initial and final configurations – in terms of (X,Y,Z) position, heading angle and flight path angle- of the vehicle are specified then shortest path computation is an interesting problem in literature. The proposed method in this thesis is based on 3D geometry and, unlike the existing iterative methods which yield suboptimal paths and are computationally more intensive, this method generates the shortest path in much less time. Due to its simplicity and low computational requirements, this approach can be implemented on a MAV in real-time. But, If the path demands very high pitch angle (as in the case of steep climbs), the generated path may not be flyable for an aerial vehicle with limited range of flight path angles. In such cases numerical methods, such as multiple shooting, coupled with nonlinear programming, are used to obtain the optimal solution. The time-optimal 3D path is also developed in the presence of wind which has a magnitude comparable to the speed of MAVs. The simulation results show path generation for a few sample cases to show the efficacy of the proposed approach as compared to the available approach in the literature.
Next, the path convergence problem is studied in 3D for MAVs. The shortest path is generated to converge to a rectilinear path and a circular path starting from a known initial position and orientation. The method is also extended to compute the time-optimal path in the presence of wind. In simulation, optimal paths are generated for a variety of cases to show the efficacy of the algorithm. The other problem discussed in this thesis considers curvature-constrained trajectory generation technique for following a series of way points in 3D space. Extending the idea used in 2D, a γ-trajectory in 3D is generated to track the maximum portion of waypoint segments with a desired shortest distance between the trajectory and the associated waypoint. Considering the flyability issue of the plane a loop-trajectory is generated which is flyable by a MAV with constrained flight path angle. Simulation results are given for illustrative purposes.
The path generation algorithms are all based on a kinematic model, considering the vehicle as a point in space. Implementing these results in a real MAV will require the dynamics of the MAV to be considered. So, a 6-DOF SIMULINK model of a MAV is used to demonstrate the tracking of the computed paths both in 2D plane and in 3D space using autopilots consisting of proportional-integral-derivative (PID )controllers .Achieving terminal condition accurately in real-time, if there is noisy measurement of wind data, is also addressed.
 
Contributor Ghosh, Debasish
 
Date 2018-04-02T15:27:41Z
2018-04-02T15:27:41Z
2018-04-02
2013
 
Type Thesis
 
Identifier http://etd.iisc.ernet.in/2005/3309
http://etd.ncsi.iisc.ernet.in/abstracts/4171/G25675-Abs.pdf
 
Language en_US
 
Relation G25675