Nanospheres Chitosan as a Targeted Drug Delivery System

Volume 1, Issue 1, 2012

ISSN: 2318-8796

International Journal of Nano Science & Technology

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IJNST International Journal of Nano Science & Technology

Volume No. 1, Issue No. 1 December - 2012

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National Printer & Publisher 18 & 22 (Basement), G-2, Tulsi Tower, Alaknanda Community Centre, New Delhi - 110 019

International Journal of Nano Science & Technology Volume No. 1,

Inaugural Issue

Number No. 1, 2012

Editorial Board Editor-in-Chief:

Chief Editor:

Prof. T R C Sinha

Prof. Dr. Techn. Murthy CHAVALI S.S.S. Yadav

Retd. Prof of Zoology B R A Bihar University S-233, 1st Floor, G.K. II New Delhi - 110 047 E-mail: [email protected]

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Associate Editors

Dr. Pervinder Kaur Department of Agronomy Punjab Agricultural University, Ludhiana, Punjab E-mail: [email protected]

Prof. Dr. Wu, Ren-jang Department of Applied Chemistry Providence University, 200 Chung-Chi Rd., Shalu 43301 Taichung, Taiwan ROC TAIWAN E-mail: [email protected] Prof. M. Sridharan Ph. D., Functional Nanomaterials & Devices Lab. Centre for Nanotechnology & Advanced Biomaterials and Dept. Electronics & Communication Engn./SEEE, Sastra University, Thanjavur-613 401, Tamil Nadu. (INDIA) E-mail: [email protected]

MEMBERS OF EDITORIAL BOARD Dr. Mihir Kumar Purkait Associate Professor, Department of Chemical Engineering Indian Institute of Technology Guwahati Guwahati-781039 Assam (INDIA) E-mail: [email protected] Dr. Masanori Kikuchi, Ph.D Group Leader, Bioceramics Group Biomaterials Unit, Nano-Bio Field International Center for Materials Nanoarchitechtonics National Institute for Materials Science E-mail: [email protected] Prof. Mandava Venkata Basaveswara Rao M. Sc., M.Tech., Ph.D. MRSC, MNASc., MACS Professor Department of Chemistry, In-Charge Department of Chemistry & Pharmacy, Krishna University, Machilipatnam – 521 001 Krishna Dist., Andhra Pradesh, India. E-mail: [email protected]; [email protected] ASSISTANT EDITORS Dr. Khushwinder Kaur H No. 447/2 Sector 45 A, Chandigarh Department of Chemistry Panjab University Chandigarh E-mail: [email protected]

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© Journal on Nano Science and Technology (IJNST). All rights reserved. No portion of material can be reproduced in part or full without the prior permission of the Editor. Note : The views expressed herein are the opinions of contributors and do not reflect the stated policies of the National Printer and Publisher. Correspondence: All enquiries, editorial, business and any other, may be addressed to: The Editor-in-chief, International Journal of Nano Science and Technology (IJNST), S-233, 1st Floor, Greater Kailash-2, New Delhi-110 048 (INDIA) • E-mail : [email protected]; [email protected] ISSN : 2318-8796

International Journal of Nano Science & Technology Number No. 1, 2012

Volume No. 1,

Contents S. No. Title

Page No.

1.

Microemulsions: A Potential Medium for Organic Synthesis Khushwinder Kaur

1

2.

Nanospheres Chitosan as a Targeted Drug Delivery System Sarvesh Kumar Pathak, Laxmi Upadhyaya, Ravi Prakash Tewari, Sandeep Kumar Pathak, Ved Kumar Mishra

25

3.

Nanotechnology and Emerging Trends in Dairy Foods: The Inside Story to Food Additives and Ingredients Kavyanjali Shukla and Krishna Kant Shukla

41

4.

Optical Properties of DC Magnetron Sputtered CdO Thin Films P. Dhivya, P. Deepak Raj and M. Sridharan

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PANi Films for Room Temperature Ammonia Sensing R. Venkatesan, P. Deepak Raj, P. Dhivya and M. Sridharan

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Studies on Curcumin Loaded Silk Fibroin Thin Films Varshini Vishwanath and M. Sridharan

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Microemulsions: A Potential Medium for Organic Synthesis Khushwinder Kaur Department of Chemistry and Centre of Advanced Studies in Chemistry Panjab University, Chandigarh – 160 014 (India) E-mail: [email protected] (Date of Receipt : 17.09.2012; Date of Acceptance for Publication: 12.11.2012)

ABSTRACT The development of new or enhanced analytical methodologies based on the use of microheterogeneous systems is a very active area of current research. The use of organized surfactant molecular assemblies, such as micelles, reverse micelles and microemulsions, in synthetic chemistry is steadily increasing because it is a greener route and results in a greatly improved analytical performance, in terms of selectivity, sensitivity and experimental convenience. This review demonstrates that how microemulsions can be a useful for (i) overcoming reactant incompatibility, (ii) speeding up reactions of one polar and one apolar reactant (microemulsion catalysis), and (iii) inducing regiospecificity. Keywords: Microheterogeneous reaction media, microemulsions, surfactants, Pseudo-phase model, water-oil-interface properties, reaction kinetics. Pages: 24

References: 87

Introduction Microemulsions [1-5] are self-aggregated systems in which oil and water are homogenously mixed due to the presence of amphiphiles. They are isotropic with typical structural units in the size range of 3-30 nm from which their transparent appearance results. They differ from conventional emulsions not only by their much smaller structural size but in particular by their thermodynamic stability, which renders them very interesting systems as they allow the formation of stabilized mixed oil/water systems, which otherwise cannot be formed.

They have been the topic of comprehensive research for more than 40 years with a particularly intense period in the late 70s and early 80s in the context of tertiary oil recovery [6]. Due to substantial improvements of experimental characterization techniques in that time, most prominently electron microscopy [7], scattering techniques like dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and, in particular, small-angle neutron scattering (SANS) [8], nuclear magnetic resonance (NMR) [9], as well as various other techniques [10,11] a good knowledge of the structure of microemulsions was obtained. As at 1

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the same time important developments in the theoretical description were advanced [12–13] a rather comprehensive picture of the properties and behavior of microemulsions has been obtained. Information concerning processes at the molecular level is obtained from conductivity, dipole moment and dielectric increment as well as NMR measurements. Complementary, the solubilization properties of AOT have been investigated phenomenologically by determining the regions of optical transparency in three or four component phase diagrams, thus, exploring the thermodynamic properties of the system. The size of the aggregates has been studied by ultracentrifugation and fluorescence depolarization studies [14].

available to constitute the microdroplet and hence only two pseudophases are considered. They consider that only for e”10 there is free water in the core of the microemulsion and hence a three-pseudophase system for the kinetic model. Other authors [22-24], using spectroscopic results like FTIR and NMR have demonstrated that there are at least three kinds of water present in the microemulsion (free water, trapped water and bounded water). From the analysis of these spectroscopic data, they found evidences that there is a significant amount of free water in all ranges, even at very small values. Other evidence against the existence of two microenvironments at small values is the possibility of obtaining nanoparticles at these small values [25-31].

In recent years, microemulsions have been explored as reaction media for a variety of organic reactions [15-18]. Being microheterogeneous mixtures of hydrocarbon, water and surfactant, they are excellent solvents for both lipophilic organic substances and polar reagents, such as inorganic salts. Performing the reaction in a microemulsion is therefore a useful way to overcome the solubility problems that are frequently encountered in organic synthesis. However, there is a controversy in the scientific community about the microstructure of water in oil microemulsions (w/o), mainly at very low water contents (w = [H2O]/[surfactant]). In fact, some authors [19] suggest that for low water contents the aggregate microstructure will deviate from the droplet model. Therefore, the pseudophase model considering the existence of three pseudophases is wrong. Correa et al. [2021] studied the reduction of ketones in AOT/isooctane/water and in AOT/toluene/water and justify the kinetic behavior considering that for small values the water properties are different from those of bulk water, being mostly bounded to the AOT-head group. For this reason, these authors assume that for < 10 in the microemulsion there is no water

An interesting aspect of the use of a microemulsion as medium for organic reactions is that not only the large oil-water interfacial area but also the choice of surfactant governs the reaction rate. The structure of microemulsion is such that when an ionic amphiphile is used as microemulsion surfactant, the interface will be highly charged. Since such a charged surfactant palisade layer requires counterions, the possibility arises to attain an accelerating effect by allowing a reagent ion to serve as counterion. Accumulation of the reacting ion in the interfacial zone will increase the probability of a reaction with the lipophilic reagent in the oil domain, thus accelerating the reaction. If the water-soluble reactant is negatively charged, e.g., hydroxyl, sulfite or some other inorganic ion, cationic surfactants will normally enhance the reaction rate (and anionic surfactants will slow down the rate) compared with the situation with only non-ionic surfactants at the interface [32]. It has also been reported that when the microemulsion is formulated with charged surfactants, the choice of counterion is also of importance for the reaction rate [33]. Highly

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polarizable anions, i.e., ions with large electron clouds, interact strongly with the oil/water interface and may make access of other ions to the interface difficult. For example, bromide, which is a common counterion for cationic surfactants, competes favorably with most other ions and unless the reagent ion is even more polarizable than bromide, the concentration of the reacting species in the interfacial region, where the reaction takes place, will be low. This type of effect of anions has been observed before at oil/water interfaces [34] and in micellar systems [35]. Thus, many reactions in microemulsion media involving lipophilic organic compounds and inorganic salts are governed not only by the choice of surfactant but also by the type of counterion present in the system.

recognized that such systems could improve oil recovery and when oil prices reached levels where tertiary recovery methods became profit earning [38]. Nowadays this is no longer the case, the other microemulsion applications are discovered, e.g., catalysts, preparation of submicron particles, solar energy conversion, liquid-liquid extraction (mineral, proteins, etc.). Together with classical applications in detergency and lubrication, the field remains sufficiently important to continue to attract a number of scientists. From the fundamental research point of view, a great deal of progress has been made in the last 20 years in understanding microemulsion properties. During the last few years extensive theoretical and experimental work has been devoted to different kind of microemulsion systems in order to build up an unambiguous picture of these systems with regard to structure and molecular processes. Parallel with this effort there has been a development of a large variety of technical applications of these systems. This present review gives an introduction to microemulsion systems and underlines the interesting aspect of this media in organic synthesis.

History The history of microemulsions has been full of ups and downs and has been involved in many heated controversies. There has been much debate about the word “microemulsion” to describe such systems. The name microemulsion itself has contributed to confusion. Microemulsions are not micro but nano and are not emulsions. They were probably discovered well before the studies of Schulman: Australian housewives have used since the beginning of last century water/eucalyptus oil/soap flake/white spirit mixtures to wash wool, and the first commercial microemulsions were probably the liquid waxes discovered by Rodawald in 1928. Microemulsions were not really recognized until the work of Hoar and Schulman in 1940, who generated a clear single phase solution by titrating a milky emulsion with hexanol [36]. The term “microemulsion” was first used even later by Schulman et al. in 1959 to describe a multiphase system consisting of water, oil, surfactant and alcohol, which forms a transparent solution [37].

Microemulsions in organic synthesis (i) Nucleophilic substitution reaction Hager et al. [39] reported the nucleophilic substitution reaction between 4-tert-butylbenzyl bromide (4-TBBB) and various iodide salts in alcohol ethoxylate (C12E5) based and sugar surfactant (C8G1).The microemulsion based on C12E5 gave a much faster reaction than that based on a C8G1. This difference is attributed to differences in water activity in the interfacial zone. The sugar-based surfactant becomes more hydrated than the alcohol ethoxylate; thus, the dielectric constant in the surfactant headgroup layer reached higher value for the former surfactant. However, for both microemulsions the rate is almost independent of the type of

Interest in microemulsions really stepped up in the late 1970’s and early 1980’s when it was

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iodide salt used. Thus, complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of 127 importance. The results from the I NMR studies, as well as from quadrupole splitting experiments performed by 2 H NMR, are indicative of a certain accumulation of the iodide ion in the interfacial zone. The 127I NMR measurements also indicate that there is a loss of iodide from the oil-water interface of the C12E5based microemulsion as the temperature is increased. This is probably due to a gradual dehydration of the oligooxyethylene chains on increasing temperature. The loss of iodide from the interfacial zone is the probable explanation to why the reaction rate in this microemulsion is not much increased when the temperature is raised. It has also been concluded that the high reactivity in microemulsions, and in particular in microemulsions based on surfactants that contain oligooxyethylene headgroups, is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such microemulsions.

detectable in the products of this work, suggesting that the reaction take place in a nonaqueous environment, i.e., at the micellar interface. It has also been found that the reaction when carried in the absence of the copolymer or CO2 under the same reaction conditions, the product yield decreases to less than 1% because microemulsion cannot be formed under these conditions. Microemulsions and emulsions based on the two-tailed cationic surfactant dioctyldimethylammonium chloride, (R2(Me)2N+Cl)-, were used to prepare sodium decyl sulfonate by Husein et al. [41]. The cationic surfactant concentrated the 2reacting anion, SO3 , at the interface and minimized the effect of phase separation and interphase mass transfer. The equilibrium between the ions exchanging at the interface was attained rapidly. The product of the reaction between the surfactant counterion, Cl-, and the decyl bromide (C10H21Br) reacted further to form the final product. At a surfactant concentration between 200 and 400 mM, the highest conversion to sodium decyl sulfonate was obtained. This concentration was sufficient to bind all of the organic substrate to the interface. Increasing the R2(Me)2N+Cl- concentration above the optimum value resulted in a decrease in the conversion due to more of the decyl chloride intermediate, which reacted more slowly, and due to the dilution effect at the interface. Increasing the concentration of C10H21Br at constant R2(Me)2N+Cl- concentration and constant initial mole ratio of Na2SO3/C10H21Br increased the average rate of formation of C10H21SO3Na since more reactants were bound to the interface and/or due to increasing the concentration of the mixed micelles. A drop in the conversion occurred, however, due to the entrapment of some C10H21Br in the oil core and/or due to the repulsion between reacting nucleophile and the product anionic surfactant. Increasing the mole ratio of Na2SO3 to C10H21Br increased the

In another report by Zhang [40] and coworkers on the nucleophilic substitution reaction between benzyl chloride (BnCl) and KBr in the CO2-induced (EO)27(PO)61(EO)27(P104)/H2O/pxylene microemulsion performed at 40 0C, the yield is much higher in microemulsion than that without microemulsion. Also, the hydrolysis reaction of BnCl did not occur, indicating that the CO2-induced microemulsion is an effective medium for the reaction. The reaction has been reported to occur at the micellar interface because KBr cannot dissolve in p-xylene and benzyl chloride is insoluble in water. Therefore, KBr exists in the water domains of the reverse micelles, and BnCl is in the p-xylene continuous phase. The hydrolysis of BnCl to form benzyl hydroxide is a competing reaction. The results of HPLC show that benzyl hydroxide was not 4

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conversion to sodium decyl sulfonate and reduced the conversion to decyl chloride. Increasing the bulk concentration of the salt, at constant R2(Me)2N+Cl- concentration, increased the interfacial concentration of NaSO3 by exchanging more Cl at the interface. Singlepseudophase model in combination with the pseudophase ion-exchange (PIE), model with three new assumptions was used to describe the sulfonation of decyl halides in microemulsion/emulsion systems. The three new assumptions employed in the current model are (1) the volume of the interfacial region varies only with the amount of surfactant, but it is not directly proportional to the surfactant concentration; (2) decyl bromide may be trapped within the oil core and not participate in the reaction if there is insufficient surfactant to bind all of the organic substrate to the interface; and (3) a single ion exchange constant accounts for the exchange between the reacting anion and the surfactant counterions. The first assumption was needed to handle high surfactant and reactant concentrations. The second assumption accounted for the retarding effect of an anionic surfactant, such as C10H21SO3Na, on nucleophilic substitution reactions. The third assumption reduced the number of fitted parameters. The model described well the experimental results over the wide range of concentrations employed for microemulsion and emulsion systems.

microemulsions is that only a modest amount of surfactant (