Keywords: intrinsic viscosity, dextrans, Mark-Houwink parameters, hydrodynamic, temperature, Journal of Polymer and Biopolymer Physics Chemistry, 2013 1 (1), The increased TEWL values which were proportional to the number of microspores indicate SC disruption and formation of microchannels in the skin. Determination of constants, kM-H and a, from the intrinsic viscosity data, requires a series of monodisperse polymer samples with known molecular weight or a series of polydisperse polymer samples with known viscosity average molecular weights, Mv. 2018;1:10915. Gums and stabilisers for the Food Industry, 5, 447-450. Ubbelohde, Leo. Anal. Here we have the hydrodynamic radius estimate for the 3kDa dextran and 1.5 kDa dextran by the Zetasizer calculator, thanks to Alan. Alan F Rawle, t A solvent at this temperature is called a theta solvent [53]. Microporations were performed 2, 5, and 10 times and the skin damage was confirmed using the TEWL measurement. Dextrans can function efficiently as anterograde or retrograde tracers, Analytes and stationary phase with Universal Calibration Relative Measurement Concentration and MW detector: RI + Viscometer Relationship between hydrodynamic volume (MW*intrinsic viscosity) and elution volume Multiple detection Therefore, the trend of "a" and kM-H decreases with T, where the presence of ethylene glycol or dimethylsulfoxide strongly changes the interactions of this solvent with the macromolecule. Determination of branching in biopolymers by size exclusion chromatography with light scattering (Malls), viscosity, and refractive index detection. Analytical Chemistry. The reason for a nonlinear Mark-Houwink relationship is confirmed by the intrinsic viscosity which in contrast with scaling prediction shows no power law behavior. With FITC-dextran 20 K, cumulative Hydrodynamic radii ( RH) were determined by dynamic light scattering. The molecular weight of dextran samples can be obtained by a variety of methods including light scattering, HPLC/SEC, sedimentation, osmometry and end-group analysis. J. Braz. To improve drug permeability, micropore ablation using RF is performed by passing an alternating electrical current through the skin at a frequency higher than 100kHz. IV. Pamis, R.; Hernndez Cifre, J. G.; Lpez Martnez, M.C. Lpez Martnez, M. C.; Daz Baos, F. G.; Ortega Retuerta, A.; Garca de , J. Journal of Chemical Education, 49(8), 577-579. Ahn, G.Y., Eo, HS., Kim, D. et al. A similar article of dextran/water [35] clearly demonstrating the dependence of Mark-Houwink parameters with temperature. Biomater Res 24, 22 (2020). Journal of Applied Polymer Science, 72, 871-876. Castellanos Gil, E. E.; Iraizoz Colarte, A.; El Ghzaoui, A.; Durand, D.; Delarbre, J.L. Soc., 16, 3A, 426-433. Determination of intrinsic viscosities of macromolecules and nanoparticles. (more or less, with a hydrodynamic radius of less than 100 nm) to cross from the vasculature into the interstitium. 2000;3(9):31826. 8. 2018 Aug 9;23(8):1984. doi: 10.3390/molecules23081984. DOI: 10.12691/jpbpc-1-1-3, Received September 18, 2013; Revised October 23, 2013; Accepted November 22, 2013. Sintov AC, Krymberk I, Daniel D, Hannan T, Sohn Z, Levin G. Radiofrequency-driven skin microchanneling as a new way for electrically assisted transdermal delivery of hydrophilic drugs. The cumulative permeation of FITC-dextran 10 K was 4.82 0.32 M, in the human skin and 5.92 0.46 M in the pig skin. The regeneration of micropores in the human cadaver skin caused by microporation was confirmed using an optical microscope and haematoxylin/eosin (H&E) staining. Carbohydrate Polymers, 38, 267-271. Table 5 shows the data of Mark-Houwink parameters determined in figure 4 from linear regressions with 2 values higher than 0.9797. The Viscosity of Dilute Solutions of Long-Chain Molecules. Google Scholar. Hrabchak C, Flynn L, Woodhouse KA. (1954). Banga AK. FITC-dextran molecular weights; 4, 10, and 20kDa molecular weight were purchased from Sigma (St. Louis, MO, USA). Determination of polymer structure by Gel Permeation Chromatography. Changes in the Mark-Houwink hydrodynamic volume of chitosan molecules in solutions of different organic acids, at different temperatures and ionic strengths. An official website of the United States government. Kirkland, J. J.; Dilks, C. H.; Rementer, S. W. (1992). This method utilizes promising strategies that have made a significant impact in transdermal delivery [6], they include: iontophoresis, microneedles, sonophoresis, radiofrequency (RF), and chemical enhancers [7,8,9,10,11]. WebThe micelles produced at pH 4.6 have a spherical shape and their size is dependent on the Maillard reaction: reaction time, molar ratio of casein to dextran, and molecular weight of dextran used. The values of 0 decreases from 2.5429 to 2.3326 x 1023mol-1 demonstrating a relative flexibility of particles. eCollection 2015. Carbohydrate Polymers 95 360-365. (1987). J Control Release. Each microporated sample was incubated in the skin culture medium. Kasaai, Mohammad R. (2012). Biological skin substitutes for wound cover and closure. Nat Biotechnol. Characterization and Classification of Dextrans from Ninety-six Strains of Bacteria. Dextran is soluble in water, methyl sulphoxide, formamide, ethylene glycol, glycerol, 4-methylmorpholine-4-oxide, and hexamethyl phosphamide [4]. A novel correlation for protein diffusion coefficients based on molecular weight on radius of gyration. Physicochemical studies of oligodextran. Saudi Pharm J. Using the polymer standards, a plot of the ln [] vs ln Mw usually gives a straight line. Granath, K. A. 10% neutral buffered formalin was purchased from Hisko (Gunpo, Korea). These studies on Mark-Houwink parameters are usually carried out at a given temperature, obtaining a consistent result but in a very limited temperature range [68]. Figure 3 shows that the parameters vary with temperature, evidencing a clear functionality of them. International Journal of Pharmaceutics, 277, 99-104. Terms and Conditions, The intrinsic viscosity classical theory of random coils at conditions []0 predicts the quotient a0 = d ln[]0/d ln M to decrease from unity to 0.5 as the chain length increases. As well as being able to measure hydrodynamic radius in the Zetasizer (if you have access to one), it's also provided with a calculator that allows Porcine wound models for skin substitution and burn treatment. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. Biotechnology Progress, 19, 544-548. Critical parameters for gel permeation All branched polysaccharide types could be described approximately by the hyperbranching theory. The dextran was chosen as another branched polysaccharide which, like the others was suspected to show hyperbranched behavior. Analyzing the values of the hydrodynamic properties of dextran in aqueous solution, it can be seen in Table 7, that all vary with the temperature. WebThomas Gutberlet works at Jlich Centre for Neutron Science (JCNS-2), Forsch and is well known for Lipoteichoic Acid, Neutron Reflectometry and Neutron Reflectivity. (1958). (2013). Just in case anyone wants to use a different molecular weight to estimate the hydrodynamic size: the calculator is integrated into the classic Zeta Pharmaceut Sci Tech. The Principle of the Suspended Level: Applications to the Measurement of Viscosity and Other Properties of Liquids. Microporation was performed 2, 5, and 10 times on each sample. 24h after microporation, the pore sizes reduced from 64.8817.20m (0h) to 48.854.27m (24h), and the pore depths reduced from 83.9120.56m (0h) to 63.9527.61m (24h). Transdermal delivery of FITC-Dextrans with different molecular weights using radiofrequency microporation, https://doi.org/10.1186/s40824-020-00201-7, http://creativecommons.org/licenses/by/4.0/, http://creativecommons.org/publicdomain/zero/1.0/. Im Tiefkhlgert (-5 bis -30C) lagern und vor Licht schtzen. Guner, A.; Kibarer, G. (2001). These results suggest that fibroblasts proliferate and migrate under the SC, and regenerate the skin. FITC-dextran solution was prepared at 1mM in PBS. Karmarkar, S.; Garber, R.: Kluza, J.; Koberda, M. (2006). HSE and DK helped to porate the skin and to measure TEWL. These values indicate for dextrans in dilute aqueous solution, both methods give very similar results of the intrinsic viscosity and the respective Mw. Kasaai, Mohammad R. (2007). Multiple Linear Least-Squares Fits with a Common Intercept: Determination of the Intrinsic Viscosity of Macromolecules in Solution. For a given polymer-solvent pair, the theta condition is satisfied at a certain temperature, called the theta () temperature or theta point. ; van Nostrum, C.F. 2021 Aug;13(4):915-925. doi: 10.1007/s12602-021-09751-1. 2013, Article ID 360239, pp. PubMedGoogle Scholar. Various average molecular weights (Mv, Mn, Mw, and Mz) instead of Mv were substituted in M-H equation. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. Interaction Parameter (); Expansion Factor (); Steric Hindrance Factor (); and Shielding Function F(); for the System PEAOrganic Solvents by Intrinsic Viscosity Measurements. Gillespie, T.; Hulme, M. A. Pathan IB, Setty CM. (more or less, with a hydrodynamic radius of less than 100 nm) to cross from the vasculature into the interstitium. A lot of research has been devoted to dextrans modification in order to describe special characteristics relevant to specific applications such as surfactants [16], as visible marker [17], polysaccharides-based nanoparticles, covalent crosslinking [18], ionic crosslinking, polyelectrolyte complex, and the self-assembly of hydrophobically modified polysaccharides, and hydrophilic modified polysaccharides [19]. ; Yevlampieva N.P. Drug Discov Today Technol. WebThis value is sensible given that i j = 0 and that the search radius of the clustering algorithm is slightly larger than the average segment length of our Dextran model (b 5.5 nm). ; Tsuchiya, H.M.; Rist, C.E. Article The micropores of the human cadaver skin were regenerated according to the time. Carbohydrate Polymers 99, 199-207. Barrier integrity was examined using Tewameter to confirm the poration of human cadaver skin using a microporation device. Alternatively, the value of qM-H can be calculated using numerical methods and other-average molecular weights (Mn, Mw, Mz) according to where c and d are empirical polynomial functions of the exponent a. Characterization of high molecular weight dextran produced by Weissella cibaria CMGDEX3. Formul. Journal of American Chemical Society, 76 (20), 5041-5052. Molecular weight, molecular weight distribution and molecular size of a native dextran. Challenges for the modern analytical ultracentrifuge analysis of polysaccharides. Chem. Masuelli, Martin A. Hydrodynamic properties of whole arabic gum. and transmitted securely. Pavlov, G.M. J Cosmet Laser Ther. To confirm the extent of skin damage and regeneration after microporation, porations were performed 2, 5, and 10 times. The formula is verified for different systems of polymer-solvent and the values are in accord with those obtained by extrapolation. The molecular mass of dextran as determined by the gel filtration and copper bicinchoninate method was approximately, 800 kDa. Ioan, C.E. The Solomon-Ciuta single-point method is used for calculating dextran intrinsic viscosity and the error relative is calculated, and %RE respect to Huggins method is >4.18% for 2000kDa, and >2.06% for 8.8kDa (Table 2). Disclaimer. The analysis of errors using the Solomon-Ciuta method is compared with HM [59]. Challenges in analysis of high-molar mass dextrans: Comparison of HPSEC, AsFlFFF and DOSY NMR spectroscopy. Dextran (DX) is one type of EPS synthesized by LAB in the presence of sucrose (R g), radius of hydrodynamic (R h), polymer conformation parameter ( = R g /R h), intrinsic viscosity ([]), Mark-Houwink coefficient () and branching degree of DXs of RPYs prepared under different conditions. Unperturbed dimensions and theta temperature of dextran in aqueous solutions. The 70-kDa FITC dextran reached the jejunum after 15 min and passed the entire small intestine within 1 h after its administration, demonstrating that 4-kDa FITC These results are in agreement with a previous study which suggested that the microporation using radiofrequency causes disruption of the SC, enabling the percutaneous permeation of the FITC-dextran [21]. Webdextran hydrodynamic radius. Carbohydrate Polymers, 36, 319-326. The equation 4 can be rearranged and resulted in a modified M-H equation as follows: where the value qM-H is the polydispersity correction factor, and it is a statistical function of the molecular weight distribution. Sci. The proportionality between []0 and M0.5 is obtained as a limiting law for the no draining regime. WebThe study of biopolymers as dextran in aqueous solution, is effectively determined by intrinsic viscosity [] measurements at different temperatures. Dextran is a branched polysaccharide, composed of -D-glucopyranosyl residues. To overcome these limitations, microporation devices that act as therapeutic vehicles for delivering drug molecules across the skin barriers have been developed. 20K groups (n=3, *: p<0.05, **: p<0.01). Curley SA. Furthermore, the influence of temperature on the intrinsic viscosity is given by the chain flexibility parameter (dln[]/dT), which gives information about the conformation of the macromolecule chain in solution [62]. Epub 2012 May 28. 10K, and c M.W. Senti, F. R.; Hellman, N. N.; Ludwig, G.; Babcock, E.; Tobin, R.; Class, C. A., (1955). Citation-(RIS Increased epidermal laser fluence through simultaneous ultrasonic microporation. Advances in Carbohydrate Analysis, 1, 63-144. Mainaa, Ndegwa Henry; Pitknen, Leena; Heikkinen, Sami; Tuomainen; Pivi; Virkki, Liisa; Tenkanen, Maija (2014). Hydrodynamic radii were measured using Dynamic Light Scattering (DLS) in a Malvern Zetasizer NanoZS DLS (Malvern Instruments, Malvern, UK) at high scattering angle (173) to minimise the effects of dust and supramolecular contamination (NIBS, 173). Antoniou, E.; Buitrago, C. F.; Tsianou, M.; Alexandridis, P. (2010). 2003;89(2):31120. The importance of this type of study lies in the analysis of the polysaccharide behavior at industrial processes, the requirements to reduce energy, avoid flow problems and product quality control. Harding, Stephen E. (1997). Figure3 shows a magnified image of human cadaver skin with microchannels formed by the microporation device (250kHz) and the skin closure over time. 2019;9(3-S):9726. WebThe invention relates to novel fluorescent dyes with multiple negatively charged groups in their ionized form which are 9-aminoacridines or 1-aminopyrene shaving of one of the fol Figure 2 shows the classical method for calculating Mark-Houwink parameters, where a linear relation between the intrinsic viscosity and the molecular weight is established for each temperature. 2015;23(3):2239. (2003). Dear Sir. Alan F Rawle , Can you help me in calculating the size of dextran 4 (molecular weight= 4000) and dextran 10 (molecular weight 10,000)? Th We will also conduct further studies on the regeneration of human cadaver skin and evaluate the possibilities of clinical trials. It is a measure of the width of molecular weight distributions (MWD) as well as probability of molecular weight distribution curve (GPC). For a limited temperature range, the viscosity of a polymer solution varies generally following a relation similar to that of usual liquids (rrhenius plot), where the polymer concentration is not very high and that temperature remains far enough from glass transition [38], and for system PEAorganic solvents see reference [63]. Food Funct. Dextran (DX) is one type of EPS synthesized by LAB in the presence of sucrose (R g), radius of hydrodynamic (R h), polymer conformation parameter ( = R g /R h), intrinsic viscosity ([]), Mark-Houwink coefficient () and branching degree of DXs of RPYs prepared under different conditions. "Dextrans in Aqueous Solution. Carbohydrate Polymers, 68, 477-488. A few percent of R (13) glucosidic linkages provides side chains which appear to be short. Herwadkar A, Banga AK. These constants can be determined experimentally by measuring the intrinsic viscosity of several polymer samples for which the molecular weight has been determined by an independent method (i.e. The molecular mass of dextran as determined by the gel filtration and copper bicinchoninate method was approximately, 800 kDa. The Mark-Houwink a constant is close to 0.5 in poor solvents. Webof overall macromolecular geometry and hydrodynamic draining. Gekko, K. (1971). Results and Discussion The microscopic dynamics of proteins are probed in a light scattering experiment. The dextran has the advantage in terms of low cytotoxicity, excellent biocompatibility, and water-solubility. However, the currently available transdermal systems are limited by low drug permeability across the skin due to the lipophilic barrier function of the stratum corneum (SC), the outermost skin layer of the skin [3,4,5]; the methods favor low molecular mass, and lipophilic molecules, making it difficult to exploit the transdermal route for large and water-soluble molecules such as proteins and peptides. 2003;10:33847. Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. A novel high dextran yielding Weissella cibaria JAG8 for cereal food application. Increased TEWL values are evidence of micropores formation. Intrinsic viscosity of bovine serum albumin conformers. J Pharm Sci. Viscosity of in water solution polysaccharides depends on intrinsic characteristics of the biopolymer (such as molecular weight, volume, size, shape, surface charge, deformation facility, esterification degree, and galacturonic content) and on ambient factors (such as pH, temperature, ionic strength, solvent, etc.). In our present study, microporated skin permeated insufficient amount of 20K FITC-dextran, suggesting that enhancement of permeability was unsuccessful with macromolecules of more than 20KM.W.. Ind. Dextrans and their derivatives find an interest in clinical applications, as well as excipients in tablets in the pharmaceutical industry [5]. Optical properties of dextran in solution and in films. Typically, the hydrodynamic diameter of the micelles is about 100 nm and the critical micelle concentration is about 10 mg/L. In addition, microporated pig skin permeated larger amounts of FITC-dextran than human skin, this can be attributed to the differences in structure between the human and pig skin; the pig skin layer is thinner (SC, 813m) than the human skin (SC, 1017m) and the pig hair follicle is longer (3871m) than the human hair follicle (18m). Markierte Dextrane sind hydrophile Polysaccharide, die hufig in mikroskopischen Studien zur berwachung der Zellteilung, zum Verfolgen der Bewegung von lebenden Zellen und zur Untersuchung der hydrodynamischen Eigenschaften der zytoplasmatischen Matrix verwendet werden. The values of Mark-Houwink parameters universalized for the range of working temperatures are the following: 0.4267 for a*, and 0.1455 cm3/g for k*M-H, with 2 of 0.9399. As intrinsic viscosity of dextrans decreases with an increase in solution temperature; chain flexibility enhances with an increase in temperature (see Table 4) showing that the intrinsic viscosity of dextran (with different molecular weights Mw from 8.8 to 200kDa) decreases linearly with an temperature increase in solution, but change to high molecular weight to hyperbranched macromolecule. The fact that the intrinsic viscosity of a given polymer sample is different according to the solvent used gives and insight about the general shape of polymer molecules in solution. (2003). Viscosity, sedimentation, and light-scattering properties of fraction of an acidhydrolyzed dextran. Part of Molecular weight, particle size and diffusion coefficient can be determined in many studies by Dynamic Light Scattering [20, 21, 22], Gel Permeation Chromatography [23], Analytical Ultracentrifuge [24, intrinsic viscosity [1, 7, 14], size exclusion chromatography / multiangle laser light scattering / differential viscometry, Flow Field-Flow Fractionation [25], and so on. ; Veldhuis, T.F.J. The first term on the left-hand side of equation 2 (i/c) has a linear relation as a function of the concentration (c in g/cm3), where is the intrinsic viscosity [] is given by (c0) [42, 43].