The Mark-Houwink parameters is calculated molecular weights range from 8.8 to 200kDa. 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. TEWL values before and immediately after microporation on human cadaver skin according to the number of times microproration was done (n=3). For rigid macromolecules, it is also conventional to combine a solution property with the volume of the particle itself, or with a quantity directly derived from it [54, 55, 56]. Part of Leiva, Angel; Muoz, Natalia; Urza, Marcela; Gargallo, Ligia; Radic, Deodato (2010). Experimental Review on Intrinsic Viscosity Measurements and Temperature Effect.". Ultimately they concluded that the temperature increment found to be an effective force in disturbing these interactions, mainly between polymer-polymer and polymer-solvent molecules for the used system. (2003). The most widely applied coatings for FDA-approved SPIONs are dextran and carboxydextran. The measurements of dextrans molecular weight were determined by size exclusion HPLC (Gilson, France) with Refraction Index detector using a Polysep-GFC-P5000 column (7.8030 mm). For a values from 0-0.5 a rigid sphere is predicted in a ideal solvent, from 0.5-0.8 a random coil in good solvent, and from 0.8-2 a rigid or rod like shape is expected (stiff chain). 2012;101(8):28619. (1954). Masuelli, Martin Alberto (2013). Colloid and Polymer Science, 286, 1223-1231. 4, 10, and 20K) was measured using the Transdermal diffusion cell system. Careers. In this study, we investigated the effectiveness of RF microporation technology in vitro, by evaluating the permeation of fluorescent-conjugated dextran (FITC-dextran) of various molecular weights through the human and pig skin after microporation, using a transdermal diffusion cell system. Thus, typically, the dextran glomerular for a molecule with a Stokes-Einstein (SE) radius of 30 is approximately sevenfold higher than that of neutral horseradish 2008;28(5):64557. Eremeeva, T. E.; Bykova, T. O. The skin poration was performed using the microporation device (LG electronics, Korea). The same way, many of these authors emphasize the non-linear or hyperbranched of dextran molecular weight range from 9 to 2000kDa [3,5,8,16, 37,38]. Middelkoop E, Bogaerdt AJ, Lamme EN, Hoekstra MJ, Brandsma K, Ulrich MMW. Amersham Biosciences, AA Edition, www.amershambiosciences.com. WebTry out PMC Labs and tell us what you think. WebAmines per 70KDa dextran Theeffectofchargerepulsiononthe hydrodynamicradiuscanbeseenwithRh increaseswithchargedensity.Charge repulsioncausesthehydrodynamicradius toincrease.Withincreasingcharge,the dextranprogressivelyunfolded.Evena lowlevelofaminationcausesthepolymer tounfold. Macromolecules, 29, 2265-2268. This low polydispersity realizes that the Mark-Houwink equation is forced at a given Mw regardless of the hyperbranched nature of the dextran molecule. The https:// ensures that you are connecting to the Lpez Martnez, M. C.; Daz Baos, F. G.; Ortega Retuerta, A.; Garca de , J. (1991). volume24, Articlenumber:22 (2020) Critical parameters for gel permeation It has been found that, when applied to water treatment, it can effectively act on refractory organic matter in wastewater through thermal decomposition and water molecular action to produce free These results suggest that fibroblasts proliferate and migrate under the SC, and regenerate the skin. Solution properties of branched dextran. The increased TEWL values which were proportional to the number of microspores indicate SC disruption and formation of microchannels in the skin. Takara, Andres; Acosta, Adolfo; Masuelli, Martin A. Curley SA. Chapter 2.1.4 Suspended level viscometers for transparent liquid, Ubbelohde Viscometer page 28-31. WebIn this work, hydrodynamic properties are investigated in different dextran aqueous solutions with different molecular weights (8.8-2000kDa), in a temperature range from 20C to 50C. Conducting a comparative analysis of the data shown in Table 1 can observer that parameter data Mark-Houwink a, obtained by these authors are very similar to that obtained in this work, which affirms its validity. The qM-H values given by equation 13, these vary from 0.9993 to 0.9841 for the range between 8.8 to 200kDa in a temperature range of 20 to 40C. For data requests, please contact the authors. The great deviation at 2000kDa occurs due to the large hyperbranched structure of the macromolecule, generating a change in its conformation and, therefore, a change in the way it flows [73]. This phenomenon is observed in the case of hyperbranched biopolymers evidencing an increase of a with temperature. For simplicity, macromolecules are treated as rigid molecules for a hydrodynamic study. (2000). 2006;3(3):37385. WebFITC Products. 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. Please enable it to take advantage of the complete set of features! Expert Rev Med Devices. Biotechnology Progress, 19, 544-548. Epub 2012 Oct 18. Lucifer yellow (LY) and FITC-labelled dextran stock solutions were prepared in Ringers-HEPES buffer (150 mM NaCl, 3.4 mM CaCl 2, 1.2 mM MgCl 2, 5.2 mM KCl, 0.5 mM NaHCO 3, 2.8 mM glucose, and 10 mM HEPES) and frozen at 20C. The effect of branching is best recognized from the molecular weight dependencies of []. The PubMed wordmark and PubMed logo are registered trademarks of the U.S. Department of Health and Human Services (HHS). After microporation, the TEWL values of the human cadaver skin increased from 11.30.6 to 33.01.0, 10.71.5 to 45.31.5, and 10.70.6 to 61.02.0g/m2/h when the microporation was performed 2, 5, and 10 times, respectively. Google Scholar. 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 The characteristic Rg/Rh value for a globular protein is ~0.775, which means that Rg is smaller than Rh. Biomacromolecules 8, 2464-2475. European Biophysical Journal, 36, 85-94. (1990). Coviello, T.; Matricardi, P.; Marianecci, C.; Alhaique, F. (2007). The Mark-Houwink a constant is close to 0.5 in poor solvents. 2012;3(1):208. 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. Biomaterials Research Journal Argentine Chemical Society 100 (2013) 25-34. J Appl Toxicol. WebTo address this perception, in the current study, FITC-dextran of different MWs (10, 70 and 150 kDa) was used to model the transdermal delivery of low MW biotherapeutics and mAbs with MWs of approximately 150 kDa. 113, 81-86. 20K groups (n=3, *: p<0.05, **: p<0.01). Huggins equation [41] gives the relation to the relative viscosity increase (i). 7 8 ; Weisz, J. Arond L.H. WebHydrodyamic Radius, R H: In addition to the analytic size of a linear (C=1) chain, the end to end distance, R eted or R 0, and the structural size, the radius or gyration, R g, dynamic measurements yield a size called the hydrodynamic radius, R H. Consider a rod particle of length L=10R where R is the radius. Radiofrequency with microneedling. 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. Advances in Carbohydrate Analysis, 1, 63-144. Enhanced topical delivery of small hydrophilic or lipophilic active agents and epidermal growth factor by fractional radiofrequency microporation. The regeneration of micropores in the human cadaver skin caused by microporation was confirmed using an optical microscope and haematoxylin/eosin (H&E) staining. Polysaccharide hydrogels for modified release formulations. TEWL measurements were taken to assess the integrity of the skin barrier and the extent of SC disruption. Universal size-independent quantities for the conformational characterization of rigid and flexible macromolecules. FOIA Format). FITC-dextran molecular weights; 4, 10, and 20kDa molecular weight were purchased from Sigma (St. Louis, MO, USA). European. and transmitted securely. Thus, it is accepted that, for every flexible-chain polymer in a (ideal) solvent, there is a universal value of 0 = 2.1-2.5x1023mol-1 [52]. There is a formula that used to calculate the radius (in Angstrom) from the molar mass (in g/mol) of dextran, a=0.33*(MM^0.46) where, a and MM are 43-1, 115-147. The molecular mass of dextran as determined by the gel filtration and copper bicinchoninate method was approximately, 800 kDa. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. Herwadkar A, Banga AK. Ghimici, Luminita; Nichifor, Marieta; Wolf, Bernhard (2009). (2013). The M-H equation is empirical and valid for monodisperse polymers, and it is applied to biomacromolecules (complex, hyperbranched, crosslink), taking the precaution of comparing the value of Mv with the polydispersity index (qM-H). Micropores are produced by the arrangement of microelectrodes on the skin at precise dimensions, then RF energy generated by alternating currents induces ionic vibrations between electrodes with positive or negative charges. Each microporated sample was incubated in the skin culture medium. Results and Discussion The microscopic dynamics of proteins are probed in a light scattering experiment. Dextran Utilization During Its Synthesis by Weissella cibaria RBA12 Can Be Overcome by Fed-Batch Fermentation in a Bioreactor. 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]. Exp Cell Res. Dextrans can function efficiently as anterograde or retrograde tracers, Armstrong, J. K.; Wenby, R. B.; Meiselman, H. J.; Fisher, T. C. (2004). The Mark-Houwink parameters and the effect of temperature on them are specifically studied. Biophysical Journal, 27, 177-181. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. These vibrations heat the skin tissue, triggering water vapor and cell ablation, forming microchannels from the SC through to the outer dermis. The slope is a value and intercept is equal to the ln kMH value [47]. WebThe Stokes radius or StokesEinstein radius of a solute is the radius of a hard sphere that diffuses at the same rate as that solute. International Journal of Biological Macromolecules, 42, 133-137. The intrinsic viscosity calculation requires several concentrations, and because of this inconvenient will not use the Huggins method in this paper. The calculated dextran molecular weights are corroborated by those tabulated data by the manufacturer with a relative error lower than 10%, being the exception dextrans 580 and 2000kDa with the highest relative error. Carbohydrate Polymers, 36, 319-326. In addition, the permeation rate was higher in pig skin than in human skin. Mark-Houwink-Kuhn-Sakurada Exponent at the Condition. The Hydrodynamic Radii of Macromolecules and Their Effect on Red Blood Cell Aggregation. The regeneration process of the skin is regulated by growth factors such as keratinocyte growth factor and fibroblast growth factor, which trigger the proliferation and migration of cells [23, 24]. Granath, K. A. It has been found that, when applied to water treatment, it can effectively act on refractory organic matter in wastewater through thermal decomposition and water molecular action to produce free We believe that the microporation device can be used as a potential technique for effective transdermal drug delivery. The receptor chamber was filled with PBS. 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. The mostly used commercial product/ polysaccharide is dextran, and it is produced from bacterium Leuconostoc mesenteroides, with an overall degree of branching of about 5% [1-3][1]. Carbohydrate Polymers, 38, 267-271. Masuelli, M. A. The microporation device based on radiofrequency can be used to enhance delivery efficiency by removing the epidermis layer. Molecular weight (M v) and hydrodynamic properties can be calculated from there. Journal Non-Newtonian Fluid Mech., 97, 295-301. Guner, Ali (1999). The numerical value of a indicates that dextrans acquire the shape of a rigid sphere in aqueous solution; and kM-H demonstrates that under water the value decreases with temperature [71, 72]. dextran hydrodynamic radius. of different origins. (2012). Deng H, Konopka CJ, Prabhu S, Sarkar S, Medina NG, Fayyaz M, Arogundade OH, Vidana Gamage HE, Shahoei SH, Nall D, Youn Y, Dobrucka IT, Audu CO, Joshi A, Melvin WJ, Gallagher KA, Selvin PR, Nelson ER, Dobrucki LW, Swanson KS, Smith AM. 2009;301(8):60913. Gold MH, Biron JA. Biodegradable dextran hydrogels crosslinked by stereocomplex formation for the controlled release of pharmaceutical proteins. 8. 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. Soc., 21, 1, 78-86. Singh TRR, Garland MJ, Cassidy CM, Migalska K, Demir YK, Ryan SAE, Woolfson D, Donnelly RF. Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. High Manufacturing Standards of Molecular Probes Dextrans. Whiteside PJD, Chininis JA, Schellenberg MW, Qian C, Hunt HK. Kasaai, M. R.; Arul, J.; Charlet, G. (2000). 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. pp13-21. Table 3 shows the intrinsic viscosity for the rest of the dextrans obtained by using the single-point method, measured at different temperatures. Determination of intrinsic viscosities of macromolecules and nanoparticles. Curvale, R.; Masuelli, M.; Perez Padilla, A. In summary, we demonstrated effective enhancement of skin permeability and delivery of macromolecules lower than 20KM.W., and regeneration of human cadaver skin after microporation with an RF-based microporation device. The lack of data on the uniformity of intrinsic viscosity measurements in the system water/dextran, highlights the significant influence of the solvent and temperature [74]. ; Talsma, H.; Hennink, W.E. Ortega, A.; Garca de la Torre, J. A similar combination involves the intrinsic viscosity and specific volume: (a/b) is called Einstein viscosity increment, and Vs is specific volume (cm3/g). Smith, David R.; Raymonda, John W. (1972). Materiaux 1-5. Webdextran fraction and the final product depend on changes in the hydrodynamic volume of the molecules after substitution. 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). Study of temperature influence. 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 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 dextran measured in plasma 1 h after its oral application is a marker of small intestinal permeability. Dextran standards with sequence molecular weight from 8.8, 40, 71.9, 110, 200, 580 and 2000 kDa were utilized for the plot of calibration curve. Comparison of single-point and dilution procedures. National Library of Medicine Accueil; Solution; Tarif; PRO; Mon compte; France; Accueil; Solution; Tarif; PRO; Mon compte The parameters of Mark-Houwink for polymers can vary with the polymer solution and temperature. Pharm Res. These studies were again focused on investigating the hydrodynamic properties of the polymer molecules, their hydrodynamic radius in relation to their radius of gyration and the coherence of the simulation results with polymer theory. With FITC-dextran 20 K, cumulative 2018;1:10915. The value of qM-H varies from one sample to another one, because it is a function of a and the average molecular weights (Mv, Mw). The effectiveness of the RF microporation technique in transdermal drug delivery of macromolecules and hydrophilic agents such as peptides, hormones, and vaccines has been demonstrated extensively in previous studies [16,17,18]. Mitragotri S. Mechanical disruption of skin barrier for vaccine delivery. 2017 Dec 12;27(1):73-78. doi: 10.1007/s10068-017-0274-0. 4K, 10K, and 20K) permeated through the human, and pig skin after microporation. Department of Biomedical-Chemical Engineering, The Catholic University of Korea, 43 Jibong-ro Wonmi-gu, Bucheon-si, Gyeonggi-do, 14662, Republic of Korea, LG electronics, 19 Yangjae-daero 11-gil, Seocho-gu, Seoul, 06772, Republic of Korea, You can also search for this author in government site. Human cadaver skins (fresh human full-thickness skin disc, 12~20mm) were supplied by Biopredic International (Saint-Grgoire, France). Cecopieri-Gmez, Martha L.; Palacios-Alquisira, Joaqun (2005). Journal of Colloid Science, 31, 308-328. Biomaterials. Progr. Environ Toxicol Pharmacol. Barrier integrity was examined using Tewameter to confirm the poration of human cadaver skin using a microporation device. The micropores were developed on pig skin and human cadaver skin with dermal and epidermal layers by the microporation device. Macromolecules. B 113, 8020-8025. Saudi Pharm J. Ibrahim O, Munavalli GS, Dover JS. The hydrodynamic radius is important in predicting transretinal penetration Carroll PJ. In Vitro Evaluation of Postbiotics Produced from Bacterial Isolates Obtained from Rainbow Trout and Nile Tilapia against the Pathogens, Dextran-Mimetic Quantum Dots for Multimodal Macrophage Imaging, Isolation of lactic acid bacteria starters from, Characterization of Antibacterial Cell-Free Supernatant from Oral Care Probiotic. Journal of Chemical Education, 49(8), 577-579. In fact, short chains do contain minor branching points. Doke SK, Dhawale SC. Peptide and protein transdermal drug delivery. The range of temperatures used was 25-50 (0.1) C and it was regulated by thermostatic bath Haake C. The viscosity measurements required Hagenbach-Couette correction time (tg 37.31s). Food Sci Biotechnol. This is because the macromolecule hydrodynamic radius changes the solution type and temperature via change in their chain exibility. Appl Biochem Biotechnol. Kumar SV, Tarun P, Kumar TA. Hennink, W.E. FITC-dextran solution was prepared at 1mM in PBS. The human skins were from the back or thigh of a 24-year-old woman. These values indicate for dextrans in dilute aqueous solution, both methods give very similar results of the intrinsic viscosity and the respective Mw. Amersham Biosciences, AA Edition, www.amershambiosciences.com. (1998). Journal of Applied Polymer Science, 13, 2031-2032. Federal government websites often end in .gov or .mil. (1969). Synthesis of dextran by dextransucrase treated, sucrose-supplemented skimmed milk revealed the promising potential of dextran as a food additive. 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 Pharm Res. Strategies to improve the potential of transdermal devices by enhancing the skin permeation of therapeutic entities. Synthesis of water-soluble and water-insoluble amphiphilic derivatives of dextran in organic medium. 2009;8(2):1739. In addition, we evaluated the regeneration of SC after microporation. Chem. ; Fran, H.P. A novel high dextran yielding Weissella cibaria JAG8 for cereal food application. The permeability of fluorescein isothiocyanate-dextrans (FITC-dextrans) with different molecular weights through the pig and human cadaver skins were measured using Franz diffusion cell. Carbohydrate Polymers, 79, 380-390. Multiple Linear Least-Squares Fits with a Common Intercept: Determination of the Intrinsic Viscosity of Macromolecules in Solution. 2004;25(9):155967. where c is the solute concentration (g/cm3), [] is the intrinsic viscosity (cm3/g), and kH represents Huggins constants (cm3/g). FITC-dextran solution (600L) was added to the donor chamber. AATEX. WebDiffusivity of 2000 kDa Dextran was significantly lower for both hydrogel formulations, but was insensitive to collagen concentration, likely due to a larger hydrodynamic diameter ( dh ~ 70 nm) on order of the collagen mesh size. 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]. Polyelectrolytes as secondary calibration standards for aqueous SEC. MeSH terms ; Bataille, B. Red blood cell rouleaux formation in dextran solution: dependence on polymer conformation. Transdermal delivery of FITC-Dextrans with different molecular weights using radiofrequency microporation. Structural characterization of a new dextran with a low degree of branching produced by Leuconostoc mesenteroides FT045B dextransucrase. Epub 2022 Feb 2. Corp. (Seoul, Korea). The Mark-Houwink a constant is close to 0.75 (or higher) for these good solvents. For 40 kDa molecules, the hydrodynamic diameter dh ~8 nm is much smaller than the collagen mesh size [ 33, 41 ]. Bahary, W. S.; Hogan, M. P.; Jilani, M.; Aronson, M. P. (1995). The particular dextrans which were used initially for conversion into synthetic blood-volume expanders [6, 7], human red blood cells aggregation for increasing the degree of polymerization and hence the molecular weight [8, 9, 10], hydrogels and microspheres [11], in drug transport system and its modifications as nanoparticles [12], in the removal through absorption of contaminant effluents such as heavy metals, organic molecules and inks [13], in the formation of biodegradable films [14, 15]. Table 2 compares the properties of nanoparticles coated with one or other polymer. Google Scholar. Sung-Wook Choi. Senti, F. R.; Hellman, N. N.; Ludwig, G.; Babcock, E.; Tobin, R.; Class, C. A., (1955). The value of P increases from 1.0272 to 1.2694 (spherical shape with tendency to spheroid for high Mw). Viscosity of Liquids. SWC designed and coordinated the research. 2012;87(6):1728. 2018 Jan;184(1):1-11. doi: 10.1007/s12010-017-2522-4. Indo AM J Pharm. Web54 we estimated that the hydrodynamic radii of 3-5 kDa dextran, 20 kDa dextran, and 70 kDa dextran are 2 55 nm, 5 nm, and 6 nm, respectively. Journal of Applied Polymer Science, 27, 795-810. The hydrodynamic 57 radius of the dextranase is 7 a Immediately after microporation, b 4h, c 8h, and d 24h (n=5, *: p<0.05). These studies were carried out at the Hisko (Gunpo, Korea). On the molecular weight distribution of dextran T-500. Ubbelohde, Leo. Ahn, G.Y., Eo, HS., Kim, D. et al. A sugar cane native dextran as an innovative functional excipient for the development of pharmaceutical tablets. California Privacy Statement, The molecular weight and Simha number do not change in this temperature range (Mw from 8.8-200kDa), P slightly change, showing modifications in the hydrodynamic properties of the biopolymer in aqueous solution as [] and RH. Biomaterials, 22, 1891-1898. The hydrodynamic radius of 2-NBDG glucose was too small to measure. 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. 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.