scholarly journals Rheological Investigation of Self-emulsification Process: Effect of Co-surfactant

2009 ◽  
Vol 12 (2) ◽  
pp. 164 ◽  
Author(s):  
Shailesh V Biradar ◽  
Ravindra S Dhumal ◽  
Ananat R. Paradkar

PURPOSE The aim of study is to investigate role of co-surfactant in self-emulsification through rheological analysis of intermediate liquid crystalline (LC) phase formed during self-emulsification. METHODS To mixture of Captex® 200P (C200) and tween 80 (T80) (SES Plain), either medium hydrocarbon chain co-surfactant (Capmul® MCM (CMCM): SES C) or long hydrocarbon chain co-surfactant (Peceol® (P): SES P) was added separately at different concentration levels. Self-emulsification was monitored by visual observations, turbidimetric and droplet size measurement. Mesophases were obtained by 30% v/v aqueous hydration of SES and characterized by polarizing microscopy, differential scanning calorimetry (DSC) and rheological studies. RESULTS SES Plain exhibited ‘bad’ emulsification owing to instantaneous gel formation in aqueous media. Almost all SES C have shown ‘good’ emulsification with transparent appearance, very low turbidity value and nano size droplets. All SES P presented ‘moderate’ emulsification with milky appearance, high turbidity value and coarse droplets. Polarizing microscopy revealed formation of lamellar phase in SES Plain and in all SES P while almost all SES C exhibited formation of micellar cubic phase. In DSC studies, higher extent of LC phase formation was observed in SES C as compared to SES P. Rheological study clearly demonstrated presence of elastic and partially recoverable mesophase in SES Plain, which was transformed into a viscous and non-recovering mesophase with addition of CMCM while there was no change in rheological status of SES Plain after addition of P. The weak and viscous LC phase in SES C must have not presented any resistance to strain induced deformation. Therefore, it might have ruptured easily and quickly, releasing jet of nanosize droplets whereas elastic mesophase in SES P might have ruptured with little resistance resulting in coarse droplets. CONCLUSION The ability of co-surfactant to promote self-emulsification was attributed to their influence on viscoelastic properties of intermediate LC phase.

2009 ◽  
Vol 12 (1) ◽  
pp. 17 ◽  
Author(s):  
Shailesh V Biradar ◽  
Ravindra S Dhumal ◽  
Anant Paradkar

PURPOSE Aim of this study is to investigate the mechanism of self-emulsification through rheological analysis of intermediate liquid crystalline (LC) phase formed during self-emulsification process. METHODS Binary system of tween 80 (T80) and imwitor 742 (I742) was used and different SES were prepared with I742 at 10, 30, 50, 70 and 90% w/w concentration levels. Self-emulsification was monitored by visual observations and droplet size measurement. Mesophases obtained by 50% v/v hydration of SES were utilized for polarizing microscopy, differential scanning calorimetry and rheological studies. RESULTS Good emulsification with nano sized droplets was observed for SES 30% as compared to micron sized droplets for other SES. In polarizing microscopy, formation of intermediate LC phase was observed in all SES. Lamellar phase was evident in 30% SES while other SES exhibited micellar cubic phase. Presence of high level of structurally bound water in thermal analysis confirmed mesophase formation in all SES. In frequency sweep, decrease in elastic modulus, and an increase in phase degree and loss tangent was observed for 30% SES. Exactly opposite trend was seen in other SES. Thus, rheological studies concluded presence of weak and fragile mesophase structure in 30% SES while LC phase structure with little structural buildup was observed in other SES. This weak mesosphere structure in SES 30% presented no or very little resistance against strain induced deformation. Therefore, during emulsification, weak mesophase in SES 30% ruptured with ease and released jet of nanosize droplets compared to coarse droplets for other SES. CONCLUSION This study signifies the effect of viscoelastic properties of intermediate LC phase on self-emulsification performance.


In this paper we give an overview of cubic liquid-crystalline mesophases formed by amphiphiles. In § 1 we present brief descriptions of the principal types of translationally ordered lyotropic phases, and describe the locations in the phase diagrams where the different types of cubic phase occur. In §2 we discuss the various forces that act between bilayers. These transverse interactions are relatively straightforward to quantify in the case of lamellar phases, but are more complex for cubic phases, because of the non-planar geometry. In §3 we show how an intrinsic desire for interfacial curvature can lead to a state of physical frustration. We then introduce the curvature elastic energy, and describe how this may be related to the stress profile across the bilayer. In the following sections we focus attention on the inverse (water-in-oil) versions of the non-lamellar phases, although analogous effects also operate in the normal topology (oil-in-water) structures. In §4 we briefly describe the inverse hexagonal phase, which is the simplest inverse phase with curved interfaces. This allows us to illustrate the role of hydrocarbon chain packing frustration in a rather clear way before coming on to the more subtle interplay between packing and curvature frustration, characteristic of the bicontinuous cubic phases, which is discussed in §5. In §6 we describe an entirely different class of cubic phases, with positive interfacial gaussian curvature. These cubic phases are composed of complex packings of discrete micellar or inverse micellar aggregates, which may be quasi-spherical and/or anisotropic in shape. Finally, in §7 we discuss geometric aspects of transitions between lamellar, hexagonal and cubic phases, and show how determination of the epitaxial relations between phases can shed light on the precise mechanisms of the phase transitions.


e-Polymers ◽  
2009 ◽  
Vol 9 (1) ◽  
Author(s):  
Shuangqing Zhang ◽  
Chaocan Zhang ◽  
Changhai He ◽  
Jun Xu

AbstractA series of polyether chelating resins with pendent biphenyl mesogenic groups were synthesized, and the chemical structure of monomers and polymers were confirmed by IR and 1H NMR detection. The thermal properties of resins were investigated by the Differential Scanning Calorimetry (DSC) and Polarizing Microscopy (POM), and the results showed that only the product of polyepichlorohydrin grafted with 4-cyano-4’-hydrobiphenyl, i.e., HPCN resin, was a kind of nematic liquid crystal polymer with typical schlieren texture (70-130 0C) and other resins were semi-crystalline. The results of adsorption experiments showed that all five resins exhibited a higher adsorption capacity (>1.0 mmol/g) for Cu (II) and Hg (II) and medium adsorption ability for Cd (II), Zn (II), Pb (II) and Co (II), however, a poor adsorption capacity (<0.3 mmol/g) for Mg (II), indicating that this type of polyether resins have a better selective adsorption for above metal ions. In addition, the adsorption capacity of HPnCP resins was generally higher than that of HPd and HPCN owing to the existence of terminal pyrrole coordination groups in HPnCP resins.


1993 ◽  
Vol 48 (6) ◽  
pp. 826-843 ◽  
Author(s):  
Gerhard Koßmehl ◽  
Frank Dirk Hoppe ◽  
Barbara Hirsch

Compounds which have two mesogenic groups with and without terminal alkyl chains containing thiophene systems, were prepared from α.ω-bis(5-formyl-2-thienyl)alkanes (3a-3n) and various aromatic amines or 2-fluorenyl-Wittig-salt (10). The liquid crystalline properties of these compounds were characterized by differential scanning calorimetry (DSC) and polarizing microscopy. Only the series of α.ω-bis{5-[N-(4′-butyloxybiphenyl-4-yl)imino]formyl-2-thienyl}alkanes (7a-71) showed enantiotropic smectic and nematic mesophases. The series of E,E-α.ω-bis[5-(2-fluorenylvinyl)-2-thienyl]alkanes (8a-81) showed enantiotropic nematic mesophases for the compounds with 4 and 6 methylene groups, monotropic nematic mesophases for the compounds with 7—12 methylene groups and no liquid crystalline phases for compounds with 3, 5, 16 methylene groups in the connecting alkylene chain. In contrast to the compounds 8a-81, E-l-(5-butyl-2-thienyl)-2-(2-fluorenyl)ethylene has a smectic mesophase.


e-Polymers ◽  
2011 ◽  
Vol 11 (1) ◽  
Author(s):  
R. N. Jana ◽  
H. Bhunia ◽  
C. Im

AbstractPhase transition behavior of silicone based liquid crystalline (LC) polymers with variable isotropic transition temperatures (Ti), synthesized from poly(methyl hydrosiloxane), 10-undecenoic acid based crosslinking agent and cholesterol based side chain mesogen, was studied by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction (XRD) measurements. The chemical structure of the mesogenic monomer and the LC polymers were confirmed by Fourier transform infra-red (FT-IR) spectroscopy and 1HNMR spectroscopy. DSC studies showed that the glass transition temperatures (Tg) and Ti of the LC polymers decreased with increasing proportion of mesogenic crosslinking agent at its low proportion and at its higher proportion Ti disappeared completely indicating that the polymeric chains had less chance to orient in the network structure. The results were consistent with the XRD and POM studies.


2007 ◽  
Vol 27 (4-5) ◽  
pp. 247-255 ◽  
Author(s):  
Nadide Kazanci ◽  
Feride Severcan

Tamoxifen (TAM) is a non-steroidal antiestrogen drug, which is widely used to prevent and treat breast, liver, pancreas and brain cancers. The present work investigates, in detail, the concentration dependent behavior of TAM (varying from 1 mol% to 45 mol%) on membrane fluidity. The differential scanning calorimetry (DSC) studies showed that tamoxifen eliminates the pre-transition and decreases the main phase transition to lower temperatures. Using visible spectroscopy at 440 nm and Fourier transform infrared (FTIR) spectroscopy it was found that membrane dynamics decreases for 1 and 3 mol% tamoxifen in both the gel and liquid crystalline phases. Above these concentrations up to 18–24 mol%, it increases and reaches its maximum values. As tamoxifen concentration was further increased, the membrane dynamics is found to be gradually decreased, although TAM still has fluidifying effect in comparison to pure phospholipid membrane. These findings are important for the effective use of tamoxifen in the cancer therapy to eliminate its dose dependent side effects reported in the literature.


2012 ◽  
Vol 8 ◽  
pp. 472-485 ◽  
Author(s):  
Govindaswamy Shanker ◽  
Marko Prehm ◽  
Carsten Tschierske

Three new types of terminally connected ABA-heterotrimesogens and heterodimesogens, composed of a bent 3,5-diphenyl-1,2,4-oxadiazole central unit and one or two rod-shaped 4-cyanobiphenyl cores or one 2-phenyl-1,3,4-thiadiazole core, connected by flexible spacers, have been synthesized, and their mesomorphic behavior was studied by optical polarizing microscopy (PM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). All dimesogens exhibit broad ranges of cybotactic nematic phases (NcybA and NcybC), in some cases accompanied by additional mesophases (CybA or SmC) at lower temperature. The combination of the 3,5-diphenyl-1,2,4-oxadiazole unit with one cyanobiphenyl core leads to the removal of tilted smectic and cybotactic nematic phases (SmC, NcybC), which are replaced by the nontilted CybA phases and nematic phases composed of SmA-type clusters (NcybA). The orthogonal cybotactic nematic phases of bent-core mesogens are of special interest for achieving biaxial nematic phases of the orthorhombic type. The orthogonal (NcybA) and skewed (NcybC) cybotactic nematic phases were distinguished by XRD and optical observations.


2020 ◽  
Vol 7 (7) ◽  
pp. 200474
Author(s):  
Xiaoxuan Wang ◽  
Zhaoxia Li ◽  
Haiying Zhao ◽  
Shufeng Chen

New azobenzene derivatives with dihydropyrazole heterocycle have been prepared and characterized. According to thermal polarizing microscopy and differential scanning calorimetry studies, the compounds consisting of four linearly linked rings and a long alkoxy chain on the azobenzene side ( 3a-8 and 3a-14 ) displayed no liquid crystal properties. When the length of mesogenic unit increased to five rings, except for compound 5a-8 , all compounds from 5a-10 to 5a-16 containing a long chain of 10–16 carbon atoms on the side of ester group displayed liquid crystalline properties, and the mesogenic domain gradually narrowed with increase of the chain length. However, in the case of the molecule with long alkoxy chains on both sides, only 5c-16 with a long chain of 16 carbon atoms exhibited liquid crystal behaviour. In addition, these azo compounds underwent isomerization from E to Z under ultraviolet irradiation and then thermal back relaxation slowly in the dark, which can be recycled many times.


Author(s):  
Afzana Anwer ◽  
S. Eilidh Bedford ◽  
Richard J. Spontak ◽  
Alan H. Windle

Random copolyesters composed of wholly aromatic monomers such as p-oxybenzoate (B) and 2,6-oxynaphthoate (N) are known to exhibit liquid crystalline characteristics at elevated temperatures and over a broad composition range. Previous studies employing techniques such as X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) have conclusively proven that these thermotropic copolymers can possess a significant crystalline fraction, depending on molecular characteristics and processing history, despite the fact that the copolymer chains possess random intramolecular sequencing. Consequently, the nature of the crystalline structure that develops when these materials are processed in their mesophases and subsequently annealed has recently received considerable attention. A model that has been consistent with all experimental observations involves the Non-Periodic Layer (NPL) crystallite, which occurs when identical monomer sequences enter into register between adjacent chains. The objective of this work is to employ electron microscopy to identify and characterize these crystallites.


Author(s):  
David M. Anderson ◽  
Tomas Landh

First discovered in surfactant-water liquid crystalline systems, so-called ‘bicontinuous cubic phases’ have the property that hydropnilic and lipophilic microdomains form interpenetrating networks conforming to cubic lattices on the scale of nanometers. Later these same structures were found in star diblock copolymers, where the simultaneous continuity of elastomeric and glassy domains gives rise to unique physical properties. Today it is well-established that the symmetry and topology of such a morphology are accurately described by one of several triply-periodic minimal surfaces, and that the interface between hydrophilic and hydrophobic, or immiscible polymer, domains is described by a triply-periodic surface of constant, nonzero mean curvature. One example of such a dividing surface is shown in figure 5.The study of these structures has become of increasing importance in the past five years for two reasons:1)Bicontinuous cubic phase liquid crystals are now being polymerized to create microporous materials with monodispersed pores and readily functionalizable porewalls; figure 3 shows a TEM from a polymerized surfactant / methylmethacrylate / water cubic phase; and2)Compelling evidence has been found that these same morphologies describe biomembrane systems in a wide range of cells.


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