Classification of vesicles by size and relative pressure difference by Laplace equation [53, 54].
\r\n\tThis book shall focus on these antisense guided sequence specific silencing molecules with different mechanisms and potency for gene silencing, providing the reader with a comprehensive overview of the current state-of-the-art in ASO based therapeutics, featuring the more recent developments in terms of clinical translation and the use of nanomedicine for the effective delivery of therapeutic nucleic acids towards precision medicine.
",isbn:null,printIsbn:"979-953-307-X-X",pdfIsbn:null,doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"96f256f5bb2e750c7496b3c0b62cb95a",bookSignature:"Prof. Pedro Baptista and Prof. Alexandra R Fernandes",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/9571.jpg",keywords:"gene therapy, gene silencing, genome modulation, post-transcriptional modulation, modified oligonucleotides, PNAs, LNAs, siRNA, antisense nucleotides, vectorization of antisense nucleotides, nanotheranostics, clinical translation, nanoparticles for gene delivery",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"October 25th 2019",dateEndSecondStepPublish:"November 15th 2019",dateEndThirdStepPublish:"January 14th 2020",dateEndFourthStepPublish:"April 3rd 2020",dateEndFifthStepPublish:"June 2nd 2020",remainingDaysToSecondStep:"a year",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:null,kuFlag:!1,biosketch:null,coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"82671",title:"Prof.",name:"Pedro",middleName:null,surname:"Baptista",slug:"pedro-baptista",fullName:"Pedro Baptista",profilePictureURL:"https://mts.intechopen.com/storage/users/82671/images/system/82671.jpg",biography:"Pedro Viana Baptista (b.1972) holds a degree in Pharmaceutical Sciences (1996) from the Universidade de Lisboa. He obtained his PhD in Human Molecular Genetics from the School of Pharmacy, University of London in 2000. In 2001 moved to FCT-NOVA where he created the Nanomedicine Group, which he leads. Currently, he is Full Professor of Molecular Genetics & Nanomedicine at the Department of Life Sciences, FCT-NOVA and responsible for the NanoImunoTech Group – Nanomedicine in the Applied Biomolecular Sciences Research Unit. His work focuses on the biomedical applications of nanoparticle-based strategies towards light-induced cancer therapy and as gene silencing platforms (including siRNA, antisense and nanobeacons). Coordinates several research projects focused on the use of nanotechnology for molecular diagnostics and nanotheranostics, including nanoparticles for diagnostics and therapy; biosensors (TFTs and ISFETs); medium-throughput SNP analysis platforms, and nanoparticle-based therapies (nanovectors for siRNA and antisense therapy, targeted combined therapies).",institutionString:"Universidade Nova de Lisboa",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"2",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"Universidade Nova de Lisboa",institutionURL:null,country:{name:"Portugal"}}}],coeditorOne:{id:"253664",title:"Prof.",name:"Alexandra R",middleName:null,surname:"Fernandes",slug:"alexandra-r-fernandes",fullName:"Alexandra R Fernandes",profilePictureURL:"https://mts.intechopen.com/storage/users/253664/images/system/253664.jpg",biography:"Alexandra R. Fernandes is an Assistant Professor at the Department of Life Sciences, FCT-NOVA where she leads the group of Cancer Therapeutics dedicated to assessing novel compounds against tumor cells and elucidate the underlying molecular mechanisms. She has obtained her PhD in Biotechnology from IST-UL and, before joining FCT-NOVA, was responsible for setting up key molecular genetics diagnostics facilities in Portugal.",institutionString:"Universidade Nova de Lisboa",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"1",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"Universidade Nova de Lisboa",institutionURL:null,country:{name:"Portugal"}}},coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"16",title:"Medicine",slug:"medicine"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"270941",firstName:"Sandra",lastName:"Maljavac",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/270941/images/7824_n.jpg",email:"sandra.m@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. From chapter submission and review, to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. 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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"878",title:"Phytochemicals",subtitle:"A Global Perspective of Their Role in Nutrition and Health",isOpenForSubmission:!1,hash:"ec77671f63975ef2d16192897deb6835",slug:"phytochemicals-a-global-perspective-of-their-role-in-nutrition-and-health",bookSignature:"Venketeshwer Rao",coverURL:"https://cdn.intechopen.com/books/images_new/878.jpg",editedByType:"Edited by",editors:[{id:"82663",title:"Dr.",name:"Venketeshwer",surname:"Rao",slug:"venketeshwer-rao",fullName:"Venketeshwer Rao"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"4816",title:"Face Recognition",subtitle:null,isOpenForSubmission:!1,hash:"146063b5359146b7718ea86bad47c8eb",slug:"face_recognition",bookSignature:"Kresimir Delac and Mislav Grgic",coverURL:"https://cdn.intechopen.com/books/images_new/4816.jpg",editedByType:"Edited by",editors:[{id:"528",title:"Dr.",name:"Kresimir",surname:"Delac",slug:"kresimir-delac",fullName:"Kresimir Delac"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"59412",title:"Recent Dispersion Technology Using Liquid Crystal",doi:"10.5772/intechopen.74156",slug:"recent-dispersion-technology-using-liquid-crystal",body:'\nIn a few decades, formulation technology in the fields of cosmetics and pharmaceutics has evolved owing to the advanced nanotechnologies involving theory, computational simulation, and analytical devices, and nowadays, various forms such as a capsule, tablet, poultice, and liquid emulsion can be designed in consideration of usability, quality assurance, as well as efficacy of an active ingredient. Colloid science is a very strong tool to understand and control these points and eventually most of formulations regardless of soft and hard matters. In addition, the stuff we are made of, blood, organ, and bone, contains colloidal particles. Since the industrial era, new kinds of colloid-containing products, including paint, foam, pastes, and so on, have been developed.
\nThe colloidal system is referred to be a system in which one phase is homogeneously dispersed in another phase. It seems to be the similar relation of solute and solvent, while this dispersion system should be little soluble mutually. Both the dispersed phase and continuous phase are in gas, liquid, solid states, and may be in liquid crystal (LC) state, and generally many industrial products can be categorized by these phase states (Figure 1) [1]. Typically, the emulsified products such as milk consist of oil (oil phase) and water (aqueous phase), namely being a liquid-liquid dispersion system. When one liquid is dispersed in another liquid, the dispersion system would be called “lotion” for a transparent solution or “emulsion” for a turbid solution. Thus, the colloid dispersion system can be classified into two types, in which one is “molecular colloid” or “association colloid,” and the other “dispersed colloid.” The molecular colloids are known to be formed in polymer solutions such as starch and protein, and the association colloids are micellar solution consisting of surfactant molecules. These two colloid systems are thermodynamically stable and spontaneously formed in a solvent, generally called “solubilizing system.” This system has been utilized for cleansing, the targeting drug delivery of a poorly soluble compound encapsulated in micelle, and so on. On the other hand, the dispersed colloid is unstable and separated into two phases sooner or later, and many of formulations, such as liquid-liquid emulsion and liquid-solid suspension, are concerned.
\nVarious colloidal dispersion systems [1].
This chapter will introduce unstable colloid dispersion systems using LC. One may have doubt on the relation between the colloid dispersion and LC. However, this intermediate state has a potential to generate new value and some liquid crystals have been already contributed to the formulation technology. Here, the following two topics will be separately mentioned because LCs are applied in different manners.
Emulsification technology using self-assemblies
LC dispersions
The first topic will explain emulsion systems stabilized by LCs and the unique properties, and note that LC can be used as a stabilizer for emulsion. The second topic may be more common for the recent researchers of LCs and will review various LC dispersions that are prospective vehicles for the drug delivery system.
\nFirst, LC used for cosmetics and pharmaceutics is explained in brief. As known well, the LC can be classified into “lyotropic” and “thermotropic” LCs, which may be defined by their dependent parameters, concentration and temperature, respectively. In some cases, they cannot be definitively distinguished by their features, for example, the nematic phase is often observed in the thermotropic LC, but a peculiar surfactant solution system forms it at certain temperature [2]. In addition, the identical LC structure may be termed independently, for example, hexagonal LC for lyotropic system and columnar LC for thermotropic one. The principal difference between two LCs is constituent; the representative compound to form the lyotropic LC is surfactant, and the thermotropic LC is formed by anisotropic molecules with a mesogen group. Some surfactants have mesogen groups in the molecule as well, whereas the important interactions in the lyotropic LC system should be solvation and hydrophobic interaction rather than molecular interactions via the mesogen group that can provide the translational order and optical anisotropy. Therefore, most of the surfactant cannot work in the absence of solvent and rarely forms LC by itself.
\nThe surfactant is paraphrased by amphiphiles which have the dual character, hydrophilicity and lipophilicity, derived from hydrophilic and lipophilic groups. The thermodynamic properties of amphiphiles in aqueous solution are controlled by the hydrophilic group to avoid contact with water, referring to “hydrophobic effect” [3]. This leads to spontaneous formation of micelle at lower concentration of surfactant (above critical micellar concentration, CMC) and generally liquid crystals at higher concentration. The formation of self-assembled bodies is predominantly determined by an entropic contribution which arises from the local structuring of water, known as iceberg structure.
\nAt high concentrations, surfactants can self-assemble into lyotropic LCs and their structures depend on the concentration. Figure 2 shows schematic structures of the series of typical lyotropic LCs formed in a surfactant system. Cubic LC is very stiff and optically isotropic, basically divided into two types: discontinuous (I1) and bicontinuous cubic LC (V1). These cubic LCs are furthermore classified into 230 kinds of the crystal lattice with symmetries called space group. The space group can be assigned by the characteristic reflection plane relevant to Miller indices. Hexagonal LC (H1) has the two-dimensional structure that the infinitely elongated rod-like micelles are packed in the hexagonal array and shows optical anisotropy. Lamellar LC (Lα) consists of one-dimensionally stacked bilayers and also shows optical anisotropy. The reverse-type micelle and LCs except for Lα are formed in the surfactant solution; reverse micelle (L2), reverse discontinuous (I2) and bicontinuous cubic LC (V2), and reverse hexagonal LC (H2).
\nSummary of self-assembly structures formed in surfactant systems, and relationship between the structure and three parameters, critical packing parameter (CPP), hydrophilic-lipophilic balance (HLB), and interfacial curvature.
A schematic phase diagram in a binary surfactant/water system is demonstrated in Figure 3, indicating that all LCs not always appear over the concentration range. The type of LC formed in the system depends on the kind of surfactant, added oil, and additive as well as surfactant concentration. Temperature is also a factor to determine the micelle and LC structure. The temperature-dependent phase transitions can be observed in Figure 3, for example, micellar solution (L1) → two phase (II), and hexagonal LC (H1) → L1. Any phase transitions in a surfactant system are always relevant to interaction between surfactant and solvent, and three important parameters, interfacial curvature, critical packing parameter (CPP), hydrophile-lipophile balance (HLB) number, prevailing in the academic and industrial fields are applied to understanding and controlling the self-assembly structures and the phase transition phenomena. The concentration-dependent LC structures can also be interpreted by these parameters.
\nSchematic phase diagram of a binary surfactant/water system. W: monodispersed solution, L1: micellar solution, H1: hexagonal LC, V1: bicontinuous LC, La: lamellar LC, S: surfactant solid, and II: two phase.
The LC structure is characterized by the interfacial curvature (main curvature). In principle, overall area on the interface can be defined as the mean curvature (H) and Gaussian curvature (G) using the radii of the main curvatures, R1 and R2
\nIn the case of a spherical micelle, which is formed at the low surfactant concentration, the mean curvature corresponds to H = 1/R (R = R1 = R2) and the Gaussian curvature is G = 1/R [2] because of its isotropic structure. On the other hand, anisotropic structures, such as cylindrical micelle and bilayer structure, give different curvatures; H = 1/(2R1) and G ~ 0 for the cylindrical structure, H ~ 0 and G ~ 0 for the bilayer structure. In general, the positive curvature indicates convex toward the water phase, and contrarily the negative one is concave. Thus, the curvature continuously changes from positive to negative or from large to small in the order corresponding to L1, I1, H1, V1, Lα, V2, H2, I2, L2 as shown in Figure 2.
\nThe LC structures are governed geometrically by the volume fraction of the self-assembly occupied in space of the solution and the molecular structure of surfactant composed in the system. The surfactant molecules can be arranged in a self-assembly under a given condition so that the interfacial area per molecule will be minimized in order to avoid the contact of the alkyl chain and water. The morphology of the self-assembly is determined by the balance of two opposing forces, hydrophobic attraction at the alkyl chain-water interface, and repulsive force between the head groups of surfactants (ionic repulsion, hydration force, steric hindrance, etc.). The interfacial free energy per surfactant molecule (\n
where K is the constant, γ is the interfacial tension, and a is the cross-sectional area of the surfactant head group at the interface. The first and second terms in the equation represent attraction and repulsion, respectively. Assuming that these interactions would operate within the same interfacial area, the optimized effective cross-sectional area per molecule (aS) is estimated from the minimum \n
Israelachivili proposed “critical packing parameter (CPP),” which allows one to predict the morphology of the self-assembly [4]. CPP has the non-dimensional unit and can be calculated using the volume of alkyl chain (VL), the length of the extended alkyl chain (l), and aS
\nCPP gives a geometric characterization of a surfactant molecule and will be seen to be very useful when discussing the type of self-organized structure formed by a given amphiphile. Considering what surfactants fall into the different categories of the self-assembly structures shown in Figure 2, we note that CPP characterizes the self-assembly structure, for example, the CPP < 1/3 for the spherical micelles (L1, I1), 1/3 ~ 1/2 for the cylindrical micelles (H1), ~1 for the bilayer structure (Lα). For the nonionic surfactant, CPP becomes smaller with increasing the polymerization degree of the hydrophilic group [5, 6, 7], indicating that curvature changes toward positive.
\nThe HLB number has been utilized as a parameter which characterizes the surfactant and would be widely spreading in the industrial field because of the chain length distribution of the commercial surfactants.
\nHLB denotes the nature of surfactant in terms of hydrophilicity and lipophilicity. Griffin [8, 9] codified the HLB numbers for nonionic surfactants. Till now, several equations have been proposed to calculate the HLB number for different surfactants including ionic surfactants [10, 11, 12, 13, 14]. Generally, the HLB number can be calculated from the hydrophilic and lipophilic portions of the molecule. The HLB number is a useful parameter for selection of surfactants suitable for various applications (e.g., emulsifier, solubilizer, wetting agent, and antifoamer).
\nSince an emulsion is a thermodynamically unstable system, the state and stability are greatly influenced by the preparation process. This can be understood from the several emulsification methods such as the phase inversion temperature (PIT) method [15], D-phase emulsification [16], quenching method [17], and liquid crystal (LC) emulsification [18], which are attributed to stability at the oil-water interface accumulated by surfactant molecules or self-assemblies.
\nThe LC emulsification method was discovered by Suzuki et al. and referred to the process that an oil phase was added directly to a lamellar liquid crystal (Lα) phase, and then dispersed by agitation to produce an emulsion (Figure 4) [18]. The key to LC method is to select an appropriate surfactant that preferentially forms Lα phase, as well as constituents of aqueous phase. According to CPP, the surfactant with a balanced HLB number, in general, a two tails surfactant tends to form Lα. This emulsification method is achieved in two steps corresponding to the arrows in Figure 4. In the first step, the oil phase is added and dispersed into the Lα phase composed of surfactant/glycerol/water. In the second step, water is poured into the oil in Lα (O/LC) to form an O/W emulsion. This LC method can form a stable emulsion because the LC phase is present as “third phase” surrounding the dispersed oil phase and physically prohibits coalescence of emulsion droplets. The stabilization mechanism of emulsion can be referred to the other emulsification technologies such as Pickering emulsification [19] and three-phase emulsification [20], collectively named “Active Interfacial Modifier (AIM)” [21, 22].
\nProcedure of LC emulsification in the ternary phase diagram of b-branched L-arginine hexyldecyl phosphate (R6R10MP-1Arg)/glycerol/oil/water system [18]. Premixture of R6R10MP-1Arg/glycerol/water forms the lamellar LC, in which oil is added then in order to form the two phase LC+O (O/LC) (first step). Finally, O/W emulsion (LC+O+W) is obtained by adding water to the O/LC solution (second step). W: water phase, O: oil phase, and LC: liquid crystal phase.
Nanoemulsions are nanosized emulsions, typically, a size of tens to hundreds nanometer, which can be expected to improve the stability of emulsion and the delivery of active ingredients. The term “nanoemulsion” also refers to a mini-emulsion which is fine oil/water or water/oil dispersion stabilized by an interfacial surfactant film. According to the droplet size, the nanoemulsions are apparently transparent or translucent [23, 24, 25]. Contrary to the microemulsions, the nanoemulsions are thermodynamically unstable, yet they may have high kinetic stability. Disruption of the nanoemulsions would be processing within hours, days, or weeks through general flocculation, coalescence, and Ostwald ripening. These characteristic properties have put the nanoemulsions to practical use, such as cosmetics [26, 27, 28], pharmaceutics [29, 30, 31, 32, 33, 34], reaction media for polymerization [35, 36], and agrochemicals [37].
\nIn industrial fields, it has been paid attention to how to formulate and prepare a stable emulsion. Two major methods for the preparation of fine emulsions are well known: dispersion or high-energy methods, and condensation or low-energy methods [23]. The high-energy method is the most popular procedures to produce a fine emulsion using specific equipment, such as high-shear stirring, high-pressure homogenization, and ultrasonication [24]. This method, however, is not preferable from the point of environmental view because of a large amount of energy loss. On the other hand, the low-energy methods utilize unique properties of surfactant and in particular the phase transitions that take place during the emulsification process as a result of a change in the spontaneous curvature of the surfactant. The phase transition with the drastic curvature change can be driven by the phase inversion temperature (PIT) method [15, 38] and the phase inversion composition (PIC) method [39]. The preparation methods of nanoemulsions have been widely reported in the nonionic and ionic surfactant systems, by using both of the high- and low-energy methods [23, 24]. Solans et al. had thoroughly investigated low-energy input methods using PIT and PIC and successfully produced finely dispersed nanoemulsions [40, 41, 42, 43, 44, 45]. It was also demonstrated that a liquid crystal formation would play an essential role in forming a fine nanoemulsion [44].
\nYamashita et al. proposed a unique nanoemulsion using a discontinuous cubic LC (I1) [46]. This nanoemulsion is simply obtained by diluting I1 without any high-energy input (Figure 5). Contrary to the common emulsions, the I1-based nanoemulsion has an abnormal shear-response: the semi-stable structure of the nanoemulsion is breaking down gradually by applying a mechanical energy (Figure 6). On the other hand, H1 and V1 do not form such transparent nanoemulsion. Such a new type of emulsion would be applicable for cosmetics and pharmaceutics as an external application. Since the solution transforms from nanoemulsion to emulsion when shearing force is applied, the solubility of active agent loaded in the hydrophobic compartment of the nanoemulsion should be varied. This can also modulate partition between the formulation and the skin surface (stratum corneum), which is a key factor for transdermal drug delivery systems [47, 48].
\nQuasi-ternary equilibrated phase diagram in the polyoxyethylene octyldodecyl ether (C12C8EOn)/water/glycerol/squalane system at 25°C (top) [46]. The weight ratio of water/glycerol is fixed at 31/69. The arrow in the phase diagram indicates the preparation route of the novel emulsion. Bottom pictures show sample appearances of the solutions prepared by (a) simple mixing and (b) dilution method utilizing the cubic liquid crystal (I1). L1: micellar solution, I1: discontinuous cubic LC, and O: excess oil (O).
Change in transmittance of the nanoemulsion formed in the polyoxyethylene octyldodecyl ether (C12C8EOn)/water/glycerol/squalane system as a function of time under different shearing rates; 3000 rpm (■), 4000 rpm (○), and 5000 rpm (●) [46]. The transmittance measurements were carried out using the monochromatic light source (l = 550 nm) at room temperature. The surfactant concentration is 1.4 wt.%.
Liquid crystal dispersions are promising drug carriers and typically referred to vesicle (liposome), cubosome, and hexosome that have two domains to accumulate both hydrophilic and lipophilic ingredients, although the micelle or reverse micelle has either compartment.
\nA vesicle is a hollow aggregate with a shell made from one or more amphiphilic bilayers. According to the number of bilayer shell, vesicles can be roughly categorized: a vesicle with a single bilayer is called “unilamellar vesicle” and the one with a shell of several bilayers is “multilamellar vesicle (MLV).” MLV is sometimes called “onion vesicle.” Figure 7 exhibits a unilamellar vesicle. Vesicles formed by lipids are termed “liposomes,” which are of great interest and have been widely studied because they are simple membrane models for cell. Vesicles or liposomes have no biological functionality, while vesicle formation and fusion should be important in many physiological processes. Liposomes are also important technology in cosmetics and for drug delivery. In both cases, the liposome acts as a delivery vehicle for active material contained inside. The aims of encapsulating the active materials (or drugs) in the liposome are mainly targeting and release control, whereby not only effective delivery but reduction of side-effect can be attained. However, this targeting technology has not been established yet, although gradually developed by recent studies such as protein recognition and stealth vehicle.
\nSchematic representation of unilamellar vesicle.
Vesicles (or liposomes) are usually not in thermodynamic equilibrium, while they can be kinetically stable for quite long period. As seen in Figure 8 [49], vesicles are formed in a two-phase region, Lα + W, where excess water is separated from the Lα phase. In such systems, the constituent molecules cannot transform to another LC when diluted with water because of their packing restriction of lipophilic chain, and instead vesicles are formed to minimize the energy loss of lamellar membrane edge (Eedge) [50, 51].
\nPhase diagram of the binary DPPC/water system [49]. La: lamellar LC, H: reverse-type hexagonal LC, Q: reverse-type bicontinuous cubic LC, Pb: flat ripple phase, Pb: non-flat ripple phase, Lb: gel phase, and W: excess water.
R is the radius of lamellar sheet (disk) and γL is the line tension. On the other hand, the bending energy (Ebend) should be required to form the vesicles, expressed by the following equation [52]:
\nwhere k is the bending modulus. When Ebend is smaller than Eedge, vesicles are preferentially formed. The unit structure of vesicle is same with Lα and CPPs of both morphologies are assigned to be nearly unity. According to the morphological similarities, the concentric Lαphase can be reversibly transformed to a multi-lamellar vesicle (MLV) by applying a certain shearing force (Figure 9) [39].
\nDynamic phase diagram of SDS/pentanol/water/dodecane system as functions of the volume fraction of bilayer (f) and shear rate (\n\n\nγ\ṅ\n\n\n) [77]. I region: defected lamellar LC, II region: multilamellar vesicle (MLV), and III region: non-defected lamellar LC.
Practically, unilamellar vesicles with different sizes are used for the drug delivery carrier and cell model, while the bilayers of these vesicles may have different physicochemical properties depending on the size. General unilamellar vesicles are listed in Table 1, where one can compare to various cell sizes [53, 54]. Regarding the topological effect of the vesicle, the surface energy depends on the curvature as expressed by Laplace equation
\nwhere Pin and Pout are the inside and outside pressure, γ is the interfacial tension, and r is the radius of curvature. As shown in Table 1, Pin for large unilamellar vesicle (LUV) and small unilamellar vesicle (SUV) are 25 and 250 times larger than giant unilamellar vesicle (GUV), respectively. In other words, Ebend of the membrane becomes larger with decreasing the vesicle size and then the molecules are less mobile and more ordered. Sakamoto suggested that the bilayer curvature had a significant effect on not only stiffness, but also function of the bilayer membrane [55].
\n\n | Size | \nRelative pressure difference \n\n | \n
Thickness of cell membrane | \nca. 5 nm | \n\n |
Small virus | \n30 nm | \n\n |
Small unilamellar vesicle (SUV) | \n~ 40 nm | \n1 | \n
Lysosomes | \n200–500 nm | \n\n |
Large unilamellar vesicle (LUV) | \n~200 nm | \n50 | \n
E. coli—a bacterium | \n2 mm | \n\n |
Human red blood cell | \n9 mm | \n\n |
Giant unilamellar vesicle (GUV) | \n10 mm | \n250 | \n
Human egg | \n100 mm | \n\n |
Many methods can be applied to prepare various vesicles, which result in different types of vesicles and size distributions [56, 57]. First of all, it should be noted that vesicles are formed in a specific composition range depending on the kind of surfactant and phospholipid used in the system, and generally in the diluted lamellar phase which refers to the region coexisting the lamellar LC (Lα) and excess water (W) in the phase diagram. In this region, vesicles can be easily prepared by simple shaking, but many of them are MLV. Sonication is typical treatment to form vesicles with single bilayer; the high-frequency sound waves can break up the inhomogeneous stacked bilayers, inducing reassembly of bilayer. Such rough preparation produces SUV with a broad size distribution since the mechanical action is very uneven. Instead, an alternative procedure can be taken to form in particular LUV and GUV, referring to the thin film method: (1) the amphiphile is dispersed in an organic solvent, (2) the organic solvent is distilled away under vacuum to form a thin film of the amphiphile, and then (3) an excess of water is added to the thin film. In addition, dialysis and filtration (extrusion) are often utilized to fractionate the different sizes of vesicles. However, these methods deliver only formation of vesicles with a desirable size and membrane structure, and further technical methods are required to attain the prospective functions of uniform vesicles such as targeting and a large encapsulating ratio.
\nCubosome and hexosome are aqueous dispersions of inverted-type bicontinuous cubic [58, 59, 60, 61, 62] and hexagonal LCs [63, 64], respectively. Such nanostructured aqueous dispersions with internal hierarchical self-assemblies have received much attention because of their potential applications such as functional food and drug carriers [65, 66, 67, 68]. Figure 10 shows one example of phase diagram in the monoolein/water system [69], where bicontinuous cubic LC (Ia3d, Pn3m) are observed in the composition and temperature ranges. In addition, likely vesicles, two phase, Pn3m + water, is present in the water-rich region where cubosome can be formed. The fully hydrated inverted-type LCs with distinctive nanostructures are internally confined in the kinetically dispersed particles upon application of high-energy input in the presence of a suitable stabilizer like surfactant [58, 59, 68]. The internal nanostructures are controlled by CPP of amphiphilic molecule and have specific curvatures H and G. These aqueous dispersions, cubosome and hexosome, are often characterized by small-angle X-ray scattering (SAXS) and cryo-TEM. As seen in Figure 11, the cryo-TEM micrograph clearly demonstrates the internal nanostructures in the dispersions [70].
\nPhase diagram of monoolein/water system [69]. FI: fluid isotropic phase, La: lamellar LC, HII: reverse-type hexagonal LC, Ia3d and Pn3m (space group): reverse-type bicontinuous cubic LC.
Cryo-TEM micrograph of cubosome [70]. The bar corresponds to 100 nm.
The feasibility of the nanostructured aqueous dispersions as drug carrier has been investigated since the 2000s, and the advantages of utilizing these dispersions have been reported, for example, solubilization of drug, bioavailability, efficient delivery, reduction of side effects, percutaneous penetration, protection of drug degradation, and release control [71, 72, 73, 74, 75, 76]. However, the number of studies on drug delivery system utilizing these dispersions is still limited regardless of the unique properties so far, and further investigations will be required to understand their potentials for drug carries and also to reveal the interaction of bioactive materials and LC carries while taking the phase behavior of LC into consideration.
\nBeyond expectation, lyotropic liquid crystals are the soft matter familiar to our life, even managing biological functions such as homeostasis in the living system. Recently, we intend to learn or mimic many things from nature to construct artificial products with some function; on the other hand, the scientific technologies that we have ever accumulated would be applicable to reveal a new mechanism of biofunction by integrating several academic fields.
\nThe formulations utilizing the liquid crystals have been contributed to the development of industry and supported our life. This may be a reason why the liquid crystals are constructed by self-assembling of numerous molecules and possess the properties of both liquid and solid. Still, there are many questions on the several applications utilizing the liquid crystals, and thus further investigations of the liquid crystals will clarify and find out unknown phenomena leading to novel functions of the liquid crystals.
\nLet
where
Boundary value problems for difference equations and impulsive differential equation have been widely received attentions from many authors (see [1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12]) and reference therein. However, as far as we know, the theory of difference equation for boundary value problems (BVPs) with impulses is rather less, there are still lots of work and research that should be done. In [3], He and Zhang obtained the criteria on the existence of minimal and maximal solutions of (1) by using the method of upper and lower solutions and monotone iterative technique. The similar techniques were applied in [11] for the problem
where
Throughout the paper, we make the following assumptions:
This paper is organized as follows. In Section 2, we introduce some preliminaries. In Section 3, by applying the fixed point theorem in cones, we obtain some new existence theorems for the impulsive difference equations with periodic boundary conditions.
Let
with the norm
Consider the following linear impulsive difference equations with periodic boundary condition
where
The following lemma transforms the analysis of PBVP (3) to the analysis of summation equation. We denote
Lemma 1. Let
where
Proof For convenience, we give the proof for the corresponding linear case (3). Consider first the homogeneous equation
which is easily solved by iteration. We have
with
or
So from (3), we see that
From (6), we have
Letting
Applying (8) and the boundary condition
Substituting (9) into (7) and using
where
Consider the PBVP (1). To define a cone, we observe that
Define
We denote the cone in
where
Since
Lemma 2. The mapping
Proof For any
Noting that
We can also obtain
Hence
The following lemma is crucial to prove our main results.
Lemma 3. (Guo
be a completely continuous operator such that either.
Then
We are now in a position to apply the preceding results to obtain the existence of positive periodic solutions to (1).
In this section, we state and prove our main findings.
Theorem 1. Suppose that the following conditions hold
Then the problem (1) has at least one positive periodic solution.
Proof
We have
where
Therefore for
Moreover
which implies
On the other hand (12) yields the existence of
where
Fixing
Thus
In particular
Consequently by Lemma 3(i), T has a fixed point in
which is a positive periodic solution of (1). The proof is complete.
Theorem 2. Suppose that the following conditions hold
Then the problem (1) has at least one positive periodic solution.
Proof We follow the same strategy and notations as in the proof of Theorem 1. Firstly, we show that for
From (13) it follows that there exists
Furthermore, we obtain
which implies
Next we show that for
where
Fixing
which implies
Finally, it follows from Lemma 3(ii) that T has a fixed point in
which is a positive periodic solution of (1). The proof is complete.
By applying the fixed point theorem in cones, we establish new existence theorems on positive periodic solutions for impulsive difference equations with periodic boundary conditions. Our main findings enrich and complement those available in the literature.
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',metaTitle:"Publication Agreement - Chapters",metaDescription:"IN TECH aims to guarantee that original material is published while at the same time giving significant freedom to our authors. For that matter, we uphold a flexible copyright policy meaning that there is no transfer of copyright to the publisher and authors retain exclusive copyright to their work.\n\nWhen submitting a manuscript the Corresponding Author is required to accept the terms and conditions set forth in our Publication Agreement as follows:",metaKeywords:null,canonicalURL:"/page/publication-agreement-chapters",contentRaw:'[{"type":"htmlEditorComponent","content":"The Corresponding Author (acting on behalf of all Authors) and INTECHOPEN LIMITED, incorporated and registered in England and Wales with company number 11086078 and a registered office at 5 Princes Gate Court, London, United Kingdom, SW7 2QJ conclude the following Agreement regarding the publication of a Book Chapter:
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\\n\\nLast updated: 2020-11-27
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The Corresponding Author (acting on behalf of all Authors) and INTECHOPEN LIMITED, incorporated and registered in England and Wales with company number 11086078 and a registered office at 5 Princes Gate Court, London, United Kingdom, SW7 2QJ conclude the following Agreement regarding the publication of a Book Chapter:
\n\n1. DEFINITIONS
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\n\nCo-Author: All other Authors of the Chapter besides the Corresponding Author.
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\n\n7.2 Third Party Rights: A person who is not a party to this Publication Agreement may not enforce any of its provisions under the Contracts (Rights of Third Parties) Act 1999.
\n\n7.3 Entire Agreement: This Publication Agreement constitutes the entire agreement between the parties in relation to its subject matter. It replaces and extinguishes all prior agreements, draft agreements, arrangements, collateral warranties, collateral contracts, statements, assurances, representations and undertakings of any nature made by or on behalf of the parties, whether oral or written, in relation to that subject matter. Each party acknowledges that in entering into this Publication Agreement it has not relied upon any oral or written statements, collateral or other warranties, assurances, representations or undertakings which were made by or on behalf of the other party in relation to the subject matter of this Publication Agreement at any time before its signature (together "Pre-Contractual Statements"), other than those which are set out in this Publication Agreement. Each party hereby waives all rights and remedies which might otherwise be available to it in relation to such Pre-Contractual Statements. Nothing in this clause shall exclude or restrict the liability of either party arising out of its pre-contract fraudulent misrepresentation or fraudulent concealment.
\n\n7.4 Waiver: No failure or delay by a party to exercise any right or remedy provided under this Publication Agreement or by law shall constitute a waiver of that or any other right or remedy, nor shall it preclude or restrict the further exercise of that or any other right or remedy. No single or partial exercise of such right or remedy shall preclude or restrict the further exercise of that or any other right or remedy.
\n\n7.5 Variation: No variation of this Publication Agreement shall be effective unless it is in writing and signed by the parties (or their duly authorized representatives).
\n\n7.6 Severance: If any provision or part-provision of this Publication Agreement is or becomes invalid, illegal or unenforceable, it shall be deemed modified to the minimum extent necessary to make it valid, legal and enforceable. If such modification is not possible, the relevant provision or part-provision shall be deemed deleted.
\n\nAny modification to or deletion of a provision or part-provision under this clause shall not affect the validity and enforceability of the rest of this Publication Agreement.
\n\n7.7 No partnership: Nothing in this Publication Agreement is intended to, or shall be deemed to, establish or create any partnership or joint venture or the relationship of principal and agent or employer and employee between IntechOpen and the Corresponding Author or any Co-Author, nor authorize any party to make or enter into any commitments for or on behalf of any other party.
\n\n7.8 Governing law: This Publication Agreement and any dispute or claim (including non-contractual disputes or claims) arising out of or in connection with it or its subject matter or formation shall be governed by and construed in accordance with the law of England and Wales. The parties submit to the exclusive jurisdiction of the English courts to settle any dispute or claim arising out of or in connection with this Publication Agreement (including any non-contractual disputes or claims).
\n\nLast updated: 2020-11-27
\n\n\n\n
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