Abstract
Loading and release behavior of a cationic dye, namely, safranine-T, through layer-by-layer (LbL) multilayered films of poly(diallyldimethylammonium chloride) (PDADMAC) and single/blend anionic polyelectrolytes (PEs), namely, poly(acrylic acid) (PAA), and poly(styrenesulfonate) (PSS), are described. The growths of PDADMAC/PSS-PAA multilayers and their safranine-T sorption behavior are monitored using the UV–Vis technique and discussed in terms of blend composition of anionic PEs and pH as well as their hydrophilicity and topography. The dye loading and desorption properties of the LbL films prepared from single/blend negatively charged PEs mainly depend on the interactions of PEs and safranine T. Strong interactions between PSS and safranine T result in a higher dye entrapping inside LbL films whereas either PAA-rich or single PAA-based LbL film exhibits larger dye desorption. A higher PSS content in the feed blend composition leads to an observable increase in θave and surface roughness whereas the use of PAA can yield a flatter surface due to its partially recomposed chain conformational structure at pH 11. Consequently, LbL multilayers obtained from single and blend polyanions can be considered as an encouraging material platform for the controlled release of charged species such as protein, drug, and dye. because of their tunable physicochemical and morphological properties as well as surface wettability.
Graphical abstract
Similar content being viewed by others
References
Picart C, Caruso F, Voegel J-C (2015) Layer-by-layer films for biomedical applications. Wiley‐VCH Verlag GmbH & Co. KGaA. https://doi.org/10.1002/9783527675869
Richardson JJ, Cui J, Björnmalm M et al (2016) Innovation in layer-by-layer assembly. Chem Rev 116:14828–14867. https://doi.org/10.1021/acs.chemrev.6b00627
Zhao S, Caruso F, Dahne L et al (2019) The future of layer-by-layer assembly: a tribute to ACS nano associate Editor Helmuth Mohwald. ACS Nano 13:6151–6169. https://doi.org/10.1021/acsnano.9b03326
Decher G, Hong J-D (1991) Buildup of ultrathin multilayer films by a self‐assembly process, 1 consecutive adsorption of anionic and cationic bipolar amphiphiles on charged surfaces. https://doi.org/10.1002/masy.19910460145
Decher G, Hong JD, Schmitt J (1991) Buildup of ultrathin multilayer films by a self-assembly process: II. consecutively alternating adsorption of anionic and cationic polyelectrolytes on charged surfaces. Thin Solid Films 210–211:831–835. https://doi.org/10.1002/bbpc.19910951122
Decher G, Schlenoff JB (2012) Multilayer thin films: sequential assembly of nanocomposite materials, Second Edition, Second. Wiley-VCH, Germany
Alkekhia D, Hammond PT, Shukla A (2020). Layer-by-layer biomaterials for drug delivery. https://doi.org/10.1146/annurev-bioeng-060418
Ghiorghita CA, Bucatariu F, Dragan ES (2019) Influence of cross-linking in loading/release applications of polyelectrolyte multilayer assemblies. A review Mater Sci Eng C 105. https://doi.org/10.1016/j.msec.2019.110050
Antipov AA, Sukhorukov GB, Donath E, Mo H (2001). Sustained release properties of polyelectrolyte multilayer capsules. https://doi.org/10.1021/jp002184
Choi J, Rubner MF (2005) Influence of the degree of ionization on weak polyelectrolyte multilayer assembly. Macromolecules 38:116–124. https://doi.org/10.1021/ma048596o
Petrov AI, Antipov AA, Sukhorukov GB (2003) Base-acid equilibria in polyelectrolyte systems: from weak polyelectrolytes to interpolyelectrolyte complexes and multilayered polyelectrolyte shells. Macromolecules 36:10079–10086. https://doi.org/10.1021/ma034516p
Du P, Zhao X, Zeng J et al (2015) Layer-by-layer engineering fluorescent polyelectrolyte coated mesoporous silica nanoparticles as pH-sensitive nanocarriers for controlled release. Appl Surf Sci 345:90–98. https://doi.org/10.1016/j.apsusc.2015.03.151
Xie M, Zhang F, Liu L et al (2018) Surface modification of graphene oxide nanosheets by protamine sulfate/sodium alginate for anti-cancer drug delivery application. Appl Surf Sci 440:853–860. https://doi.org/10.1016/j.apsusc.2018.01.175
Kolasińska M, Warszyński P (2005) The effect of nature of polyions and treatment after deposition on wetting characteristics of polyelectrolyte multilayers. In: Applied Surface Science. Elsevier, pp 759–765. https://doi.org/10.1016/j.apsusc.2005.02.060
Deligöz H, Tieke B (2014) QCM-D study of layer-by-layer assembly of polyelectrolyte blend films and their drug loading-release behavior. Colloids Surfaces A Physicochem Eng Asp 441:725–736. https://doi.org/10.1016/j.colsurfa.2013.10.033
Crespilho FN, Zucolotto V, Brett CMA et al (2006) Enhanced charge transport and incorporation of redox mediators in layer-by-layer films containing PAMAM-encapsulated gold nanoparticles. J Phys Chem B 110:17478–17483. https://doi.org/10.1021/jp062098v
Seo J, Lutkenhaus JL, Kim J et al (2008) Effect of the layer-by-layer (LbL) deposition method on the surface morphology and wetting behavior of hydrophobically modified PEO and PAA LbL films. Langmuir 24:7995–8000. https://doi.org/10.1021/la800906x
Yu D, Dai L (2010) Self-assembled graphene/carbon nanotube hybrid films for supercapacitors. J Phys Chem Lett 1:467–470. https://doi.org/10.1021/jz9003137
Zhang M, Yan Y, Gong K et al (2004) Electrostatic layer-by-layer assembled carbon nanotube multilayer film and ıts electrocatalytic activity for O 2 reduction. Langmuir 20:8781–8785. https://doi.org/10.1021/la048923l
Caruso F, Lichtenfeld H, Donath E, Möhwald H (1999) Investigation of electrostatic interactions in polyelectrolyte multilayer films: binding of anionic fluorescent probes to layers assembled onto colloids. Macromolecules 32:2317–2328. https://doi.org/10.1021/ma980674i
Niu J, Shi F, Liu Z et al (2007) Reversible disulfide cross-linking in layer-by-layer films: preassembly enhanced loading and pH/reductant dually controllable release. Langmuir 23:6377–6384. https://doi.org/10.1021/la063670c
Volodkin D, Skirtach A, Möhwald H (2010) LbL films as reservoirs for bioactive molecules. Adv Polym Sci 240:135–161. https://doi.org/10.1007/12_2010_79
Richardson JJ, Björnmalm M, Caruso F (2015) Technology-driven layer-by-layer assembly of nanofilms. Science (80-. ). 348. https://doi.org/10.1126/science.aaa2491.
Bag E, Begik O, Yusan P, Erel-Goktepe I (2015) Hydrogen-bonded multilayers with controllable pH-induced disintegration kinetics for controlled release applications from surfaces. J Macromol Sci Part A Pure Appl Chem 52:286–298. https://doi.org/10.1080/10601325.2015.1007274
Correa S, Dreaden EC, Gu L, Hammond PT (2016) Engineering nanolayered particles for modular drug delivery. J Control Release 240:364–386. https://doi.org/10.1016/j.jconrel.2016.01.040
Zhou J, Pishko MV, Lutkenhaus JL (2014) Thermoresponsive layer-by-layer assemblies for nanoparticle-based drug delivery. Langmuir 30:5903–5910. https://doi.org/10.1021/la501047m
Delcea M, Möhwald H, Skirtach AG (2011) Stimuli-responsive LbL capsules and nanoshells for drug delivery. Adv Drug Deliv Rev 63:730–747. https://doi.org/10.1016/j.addr.2011.03.010
Kurapati R, Groth TW, Raichur AM (2019) Recent developments in layer-by-layer technique for drug delivery applications. ACS Appl. Bio Mater. https://doi.org/10.1021/acsabm.9b00703
Wood KC, Boedicker JQ, Lynn DM, Hammond PT (2005) Tunable drug release from hydrolytically degradable layer-by-layer thin films. Langmuir 21:1603–1609. https://doi.org/10.1021/la0476480
Iost RM, Crespilho FN (2012) Layer-by-layer self-assembly and electrochemistry: applications in biosensing and bioelectronics. Biosens Bioelectron 31:1–10. https://doi.org/10.1016/j.bios.2011.10.040
Yut A, Caruso F (2003) Thin films of polyelectrolyte-encapsulated catalase microcrystals for biosensing. Anal Chem 75:3031–3037. https://doi.org/10.1021/ac0340049
Deshmukh PK, Ramani KP, Singh SS et al (2013) Stimuli-sensitive layer-by-layer (LbL) self-assembly systems: targeting and biosensory applications. J Control Release 166:294–306. https://doi.org/10.1016/j.jconrel.2012.12.033
Mariani S, Robbiano V, Strambini LM et al (2018) Layer-by-layer biofunctionalization of nanostructured porous silicon for high-sensitivity and high-selectivity label-free affinity biosensing. Nat Commun 9. https://doi.org/10.1038/s41467-018-07723-8
Hu M, Mi B (2013) Enabling graphene oxide nanosheets as water separation membranes. Environ Sci Technol 47:3715–3723. https://doi.org/10.1021/es400571g
Liu S, Montazami R, Liu Y et al (2010) Influence of the conductor network composites on the electromechanical performance of ionic polymer conductor network composite actuators. Sensors Actuators, A Phys 157:267–275. https://doi.org/10.1016/j.sna.2009.11.022
Liu S, Montazami R, Liu Y et al (2009) Layer-by-layer self-assembled conductor network composites in ionic polymer metal composite actuators with high strain response. Appl Phys Lett 95. https://doi.org/10.1063/1.3179554
Andre RS, Shimizu FM, Miyazaki CM et al (2017) Hybrid layer-by-layer (LbL) films of polyaniline, graphene oxide and zinc oxide to detect ammonia. Sensors Actuators, B Chem 238:795–801. https://doi.org/10.1016/j.snb.2016.07.099
Shen Y, Liu J, Jiang J et al (2003) Fabrication of a metalloporphyrin-polyoxometalate hybrid film by a layer-by-layer method and ıts catalysis for hydrogen evolution and dioxygen reduction. J Phys Chem B 107:9744–9748. https://doi.org/10.1021/jp035274y
Ferreira M, Fiorito PA, Oliveira ON, Córdoba De Torresi SI (2004) Enzyme-mediated amperometric biosensors prepared with the Layer-by-Layer (LbL) adsorption technique. Biosens Bioelectron 19:1611–1615. https://doi.org/10.1016/j.bios.2003.12.025
Lin HJ, Li T, Huang MH et al (2019) Modulating unidirectional charge transfer via in situ etching-accompanied layer-by-layer self-assembly toward multifarious photoredox catalysis. J Phys Chem C 123:28066–28080. https://doi.org/10.1021/acs.jpcc.9b08738
Shin SR, Aghaei-Ghareh-Bolagh B, Gao X et al (2014) Layer-by-layer assembly of 3D tissue constructs with functionalized graphene. Adv Funct Mater 24:6136–6144. https://doi.org/10.1002/adfm.201401300
Kim K, Ryu JH, Lee DY, Lee H (2013) Bio-inspired catechol conjugation converts water-insoluble chitosan into a highly water-soluble, adhesive chitosan derivative for hydrogels and LbL assembly. Biomater Sci 1:783–790. https://doi.org/10.1039/c3bm00004d
Tang Z, Wang Y, Podsiadlo P, Kotov NA (2006) Biomedical applications of layer-by-layer assembly: From biomimetics to tissue engineering. Adv Mater 18:3203–3224. https://doi.org/10.1002/adma.200600113
Min J, Choi KY, Dreaden EC et al (2016) Designer dual therapy nanolayered ımplant coatings eradicate biofilms and accelerate bone tissue repair. ACS Nano 10:4441–4450. https://doi.org/10.1021/acsnano.6b00087
Cheng G, Yin C, Tu H et al (2019) Controlled co-delivery of growth factors through layer-by-layer assembly of core shell nanofibers for ımproving bone regeneration. ACS Nano 13:6372–6382. https://doi.org/10.1021/acsnano.8b06032
Ma W, Zhang Y, Li F et al (2019) Layer-by-layer assembly and electrochemical study of Alizarin Red S-based thin films. Polymers (Basel) 11. https://doi.org/10.3390/polym11010165
Jiang S, Chen X, Liu M (2004) The pH stimulated reversible loading and release of a cationic dye in a layer-by-layer assembled DNA/PAH film. J Colloid Interface Sci 277:396–403. https://doi.org/10.1016/j.jcis.2004.04.008
Şenel M, Ebru Koç F (2020) Controlled release of methylene blue from layer-by-layer assembled chitosan/polyacrylic acid. Int J Polym Mater Polym Biomater 69:258–262. https://doi.org/10.1080/00914037.2018.1563082
Wang B, Gao C, Liu L (2005) Loading and release behaviors of compressed polyelectrolyte multilayers for small dye molecules. J Phys Chem B 109:4887–4892. https://doi.org/10.1021/jp0450282
Schneider G, Decher G, Nerambourg N et al (2006) Distance-dependent fluorescence quenching on gold nanoparticles ensheathed with layer-by-layer assembled polyelectrolytes. Nano Lett 6:530–536. https://doi.org/10.1021/nl052441s
Ghosh I, Das B, Nath RK et al (2016) Spectroscopic characterization of Niagara blue dye in the restricted geometry of layer-by-layer self-assembled films. Surf Rev Lett 23. https://doi.org/10.1142/S0218625X16500566
Nath J, Deb S, Bhattacharjee D, Nath RK (2011) Formation and characterization of anionic dye-polycation molecular films by layer-by-layer adsorption process. Mol Cryst Liq Cryst 548:96–106. https://doi.org/10.1080/15421406.2011.590371
Ding C, Xu S, Lin J et al (2012) Controlled loading and release of methylene blue for hydrogen-bonded LbL poly(vinyl pyrrolidone)/poly (acrylic acid) film. J Polym Res 19. https://doi.org/10.1007/s10965-011-9817-x
Ding C, Xu S, Wang J et al (2012) Controlled loading and release of methylene blue in layer-by-layer assembled polyelectrolyte films. Mater Sci Eng C 32:670–673. https://doi.org/10.1016/j.msec.2012.01.005
Gu R, Yuan X, Wu R et al (2014) Layer-by-layer assembled hydrogel nanocomposite film with a high loading capacity. J Appl Polym Sci 131. https://doi.org/10.1002/app.39352
Tedeschi C, Caruso F, Möhwald H, Kirstein S (2000) Adsorption and desorption behavior of an anionic pyrene chromophore in sequentially deposited polyelectrolyte-dye thin films. J Am Chem Soc 122:5841–5848. https://doi.org/10.1021/ja994029i
Vidyasagar A, Sung C, Losensky K, Lutkenhaus JL (2012) PH-dependent thermal transitions in hydrated layer-by-layer assemblies containing weak polyelectrolytes. Macromolecules 45:9169–9176. https://doi.org/10.1021/ma3020454
Lundin M, Solaqa F, Thormann E et al (2011) Layer-by-layer assemblies of chitosan and heparin: Effect of solution ionic strength and pH. Langmuir 27:7537–7548. https://doi.org/10.1021/la200441u
Vidyasagar A, Sung C, Gamble R, Lutkenhaus JL (2012) Thermal transitions in dry and hydrated layer-by-layer assemblies exhibiting linear and exponential growth. ACS Nano 6:6174–6184. https://doi.org/10.1021/nn301526b
Sung C, Vidyasagar A, Hearn K, Lutkenhaus JL (2012) Effect of thickness on the thermal properties of hydrogen-bonded LbL assemblies. Langmuir 28:8100–8109. https://doi.org/10.1021/la301300h
Dreaden EC, Morton SW, Shopsowitz KE et al (2014) Bimodal tumor-targeting from microenvironment responsive hyaluronan layer-by-layer (LbL) nanoparticles. ACS Nano 8:8374–8382. https://doi.org/10.1021/nn502861t
Ding C, Xu S, Wang J et al (2012) Controlled loading and release of methylene blue from LbL polyurethane/poly(acrylic acid) film. Polym Adv Technol 23:1283–1286. https://doi.org/10.1002/pat.2044
Yılmaz Aykut D, Yolaçan Ö, Deligöz H (2020) pH stimuli drug loading/release platforms from LbL single/blend films: QCM-D and in-vitro studies. Colloids Surfaces A Physicochem Eng Asp 602:125113. https://doi.org/10.1016/j.colsurfa.2020.125113
Ergün A, Tümer EH, Cengiz HY, Deligöz H (2020) Monitoring the salt stability of layer-by-layer self-assembled films from polyelectrolyte blends by quartz crystal microbalance-dissipation and their ıon separation performances. Polym Eng Sci. https://doi.org/10.1002/pen.25356
Arslan M, Dönmez G, Ergün A et al (2020) Preparation, characterization, and separation performances of novel surface modified LbL composite membranes from polyelectrolyte blends and MWCNT. Polym Eng Sci 60:341–351. https://doi.org/10.1002/pen.25289
Deniz M, Deligöz H (2019) Flexible self-assembled polyelectrolyte thin films based on conjugated polymer: quartz cristal microbalance dissipation (QCM-D) and cyclic voltammetry analysis. Colloids Surfaces A Physicochem Eng Asp 563:206–216. https://doi.org/10.1016/j.colsurfa.2018.12.014
Quinn A, Tjipto E, Yu A et al (2007) Polyelectrolyte blend multilayer films: surface morphology, wettability, and protein adsorption characteristics. Langmuir 23:4944–4949. https://doi.org/10.1021/la0634746
Liu L, Pan Y, Zhao Y et al (2020) Self-assembly of phosphonate-metal complex for superhydrophobic and durable flame-retardant polyester–cotton fabrics. Cellulose 27:6011–6025. https://doi.org/10.1007/s10570-020-03148-z
Ospanova A, Savdenbekova B, Kubasheva Z et al (2020) Several features of producing polyelectrolyte-based nanolayers by the multi-layer assembly. Mater Today Proc 31:584–587. https://doi.org/10.1016/j.matpr.2020.07.070
Ramos JJI, Llarena I, Moya SE (2011) Unusual collapse of highly hydrated polyelectrolyte multilayers with the ionic strength. J Polym Sci Part A Polym Chem 49:2346–2352. https://doi.org/10.1002/pola.24662
Han L, Mao Z, Wuliyasu H et al (2012) Modulating the structure and properties of poly(sodium 4-styrenesulfonate)/ poly(diallyldimethylammonium chloride) multilayers with concentrated salt solutions. Langmuir 28:193–199. https://doi.org/10.1021/la2040533
Wang Y, Lin C, Wang Z et al (2019) Magnetic hollow poly(cyclotriphosphazene-co-4,4′-sulfonyldiphenol)-Fe3O4 hybrid nanocapsules for adsorbing Safranine T and catalytic oxidation of 3,3′,5,5′-tetramethylbenzidine. J Colloid Interface Sci 556:278–291. https://doi.org/10.1016/j.jcis.2019.08.073
Gopalakrishnan A, Mathew ML, Chandran J et al (2015) Sustainable polyelectrolyte multilayer surfaces: possible matrix for salt/dye separation. ACS Appl Mater Interfaces 7:3699–3707. https://doi.org/10.1021/am508298d
Iturri Ramos JJ, Stahl S, Richter RP, Moya SE (2010) Water content and buildup of poly(diallyldimethylammonium chloride)/poly(sodium 4-styrenesulfonate) and poly(allylamine hydrochloride)/poly(sodium 4-styrenesulfonate) polyelectrolyte multilayers studied by an in situ combination of a quartz crystal microb. Macromolecules 43:9063–9070. https://doi.org/10.1021/ma1015984
Alonso T, Irigoyen J, Iturri JJ et al (2013) Study of the multilayer assembly and complex formation of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(acrylic acid) (PAA) as a function of pH. Soft Matter 9:1920–1928. https://doi.org/10.1039/c2sm26884a
Quinn A, Such GK, Quinn JF, Caruso F (2008) Polyelectrolyte blend multilayers: a versatile route to engineering interfaces and films. Adv Funct Mater 18:17–26. https://doi.org/10.1002/adfm.200700472
Slavgorodska M, Kyrychenko A (2020) Structure and dynamics of pyrene-labeled poly(Acrylic acid): Molecular dynamics simulation study. Chem Chem Technol 14:76–80. https://doi.org/10.23939/chcht14.01.076
Funding
The Scientific and Technological Research Council of Turkey (Grant 112M290) and Scientific Research Projects Coordination Unit of Istanbul University—Cerrahpaşa (Grant numbers 37682) provided the funding for this study.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Yılmaz Aykut, D., Yolaçan, Ö., Kaşgöz, H. et al. Tunable safranine T release from LbL films of single/blend polyanions. Colloid Polym Sci 299, 1605–1616 (2021). https://doi.org/10.1007/s00396-021-04883-w
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00396-021-04883-w