Nanoarchitecture of layer-by-layer (LbL) films is a convenient and simple way to control the photoelectrochemical properties of the semiconductor films. Hereby, we used the combination of polystyrenesulfonate (PSS) and polyethyleneimine (PEI) deposited on the TiO2 film for controlling the photochemical response of the hybrid system. Photogenerated protons on the TiO2 surface are responsible for the acidity change near the irradiated surface. We investigated that the photogenerated protons being absorbed by PEI spatially separated from the TiO2 surface with the nanoscale-thick PSS layer (with thickness ca. 5 nm) lead to the sufficient decrease in photoactivity of the hybrid system TiO2/PSS/PEI ca. 4 times in comparison with pristine TiO2. PEI nanolayer being deposited directly on the TiO2 surface can decrease the photoactivity of the system ca. 2–2.5 times.
Deposition of TiO2 photoactive layer by inkjet printing.
Investigation of photoactivity of the hybrid system based on titanium dioxide and polyelectrolyte layers (polystyrenesulfonate PSS, polyethyleneimine PEI).
Variation in “proton sponge” activity of PEI depending on the distance from TiO2 surface.
PEI nanolayer being deposited directly on the TiO2 surface can decrease the photoactivity of the system ca. 2–2.5 times, nanoarchitecture PSS/PEI – 4–4.5 times in comparison with pristine TiO2.
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Decher G, Schlenoff JB (2006) Multilayer thin films: sequential assembly of nanocomposite materials. Wiley-VCH, Weinheim
Mauser T, Dejugnat C, Sukhorukov G (2004) Reversible pH-dependent properties of multilayer microcapsules made of weak polyelectrolytes. Macromol Rap Commun 25:1781–1785
Andreeva DV, Sviridov DV, Masik A, Möhwald H, Skorb EV (2012) Nanoengineered metal surface capsules: construction of a metal-protection system. Small 8:820–825
Ilyas S, de Grooth J, Nijmeijer K, de Vos WM (2014) Multifunctional polyelectrolyte multilayers as nanofiltration membranes and as sacrificial layers for easy membrane cleaning. J Colloid Interface Sci 446:386–393
Jiang B, Barnett JB, Li B, (2009) Advances in polyelectrolyte multilayer nanofilms as tunable drug delivery systems Nanotechnol Sci Appl 2:21–27
Séon L, Lavalle P, Schaaf P, Boulmedais F (2015) Polyelectrolyte multilayers: a versatile tool for preparing antimicrobial coatings. Langmuir 31(47):12856–12872
Minnikanti S, Gangopadhyay, Reyes DR (2014) Polyelectrolyte multilayers in microfluidic systems for biological applications. Polymers 6(8):2100–2115
Berwald S & Meier-Haack J (2002). In: Tripathy SK, Kumar J, Nalwa HS (eds) Applications of polyelectrolytes and theoretical models. American Scientific Publication, Stevenson Ranch, CA
Decher G (1997) Fuzzy nanoassemblies: toward layered polymeric multicomponents. Science 277(5330):1232–1237
Richardson JJ, Bjornmalm M, Caruso F (2014) Technology-driven layer-by-layer assembly of nanofilms. Science 348:aaa2491
Grubb PM, Subbaraman H, Park S, Akinwande D, Chen RT (2017) Inkjet printing of high performance transistors with micron order chemically set gaps. Sci Rep 1202. https://doi.org/10.1038/s41598-017-01391-2
Alamán J, Alicante R, Peña JI, Sánchez-Somolinos C (2016) Inkjet printing of functional materials for optical and photonic applications. Materials (Basel) 9(11):910
Gao M, Li L, Song Y (2017) Inkjet printing wearable electronic devices. J Mater Chem C 5:2971–2993
Mehta S, Murugeson S, Prakash BD (2016) Microbes based printing for fabrication of microlenses for organic light emitting diodes. Org Electron 35:199–207
Safaryan SM, Yakovlev AV, Vinogradov AV, Vinogradov VV (2017) Inkjet printing of the chromogen free oxidase based optical biosensors. Sens Actuators B: Chem 251:746–752
Yakovlev AV, Milichko AV, Vinogradov VV, Vinogradov AV (2016) Inkjet color printing by interference nanostructures. ACS Nano 10:3078–3086
Langlet M, Kim A, Audier M, Herrmann J (2002) Sol–gel preparation of photocatalytic TiO2 films on polymer substrates. J Sol–Gel Sci Technol 25:223–234
Maltanava HM, Poznyak SK, Andreeva DV, Quevedo MC, Bastos AC, Tedim J, Ferreira MGS, Skorb EV (2017) Light-induced proton pumping with a semiconductor: vision for photoproton lateral separation and robust manipulation. ACS Appl Mater Interf 9(28):24282–24289
Gensel J, Borke T, Pazos-Perez N, Fery A, Andreeva DV, Betthausen E, Müller AHE, Möhwald H, Skorb EV (2012) Cavitation engineered 3D sponge networks and their application in active surface construction. Adv Mater 24:985
Ulasevich SA, Brezhneva N, Zhukova Y, Möhwald H, Fratzl P, Schacher FH, Sviridov DV, Andreeva DV, Skorb EV (2016) Switching the stiffness of polyelectrolyte assembly by light to control behavior of supported cells. Macromol Biosci 16:1422–1431
Andreeva DV, Melnyk I, Baidukova O, Skorb EV (2016) Local pH gradient initiated by light on TiO2 for light-triggered modulation of polyhistidine-tagged proteins. ChemElectroChem 3:1306–1310
Andreeva DV, Kollath A, Brezhneva N, Sviridov DV, Cafferty BJ, Möhwald H, Skorb EV (2017) Using a chitosan nanolayer as an efficient pH buffer to protect pH-sensitive supramolecularassemblies. PhysChemChemPhys 19:23843–23848
Moffatt S, Wiehle S, CristianoR J (2016) A multifunctional PEI-based cationic polyplex for enhanced systemic p53-mediated gene therapy. Gene Ther 13:1512–1523
Liang W-J, Wang F, Wen M, Jian J-X, Wang X-Z, Chen B, Tung C-H, Wu L-Z, (2015) Branched polyethylenimine improves hydrogen photoproduction from a CdSe quantum dot/[FeFe]-hydrogenase mimic system in neutral aqueous solutions. Chem - A Eur J 21(8):3187–3192
Park SH, Yang HN, Lee DC, Park KW, Kim WJ (2014) Electrochemical properties of polyethyleneimine-functionalized Pt-PEI/carbon black as a catalyst for polymer electrolyte membrane fuel cell. ElectrochimActa 125:141–148
Nakamura M, Sato N, Hoshi N, Sakata O (2011) Outer Helmholtz plane of the electrical double layer formed at the solid electrode-liquid interface ChemPhysChem 12:1430–1434
Skorb EV, Ustinovich EA, Kulak AI, Sviridov DV (2008) Photocatalytic activity of TiO2:In2O3nanocomposite films towards the degradation of arylmethane and azo dyes. JPhotochemPhotobiol A: Chem 193:97–102
Maltanava H, Poznyak SK, Andreeva DV, Quevedo MC, Bastos AC, Tedim J, Ferreira MGS, Skorb EV (2017) Light induced proton pumping with a semiconductor: vision for PhotoProton lateral separation and robust manipulation. ACS Appl Mater Interfaces 9:24282–24289
Yakovlev AV, Milichko VA, Vinogradov VV, Vinogradov AV (2016) Inkjet color printing by interference nanostructures. ACS Nano 10(3):3078–3086
Skorb EV, Möhwald H, Andreeva DV (2017) How can one controllably use of natural ΔpH in polyelectrolyte multilayers? Adv Mater Interfaces 4(1):1600282. 1-15
The work was supported by RSCF grant no. 17-79-20186 (formation and study of photoactivity of hybrid structures).
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The authors declare that they have no conflict of interest.
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Brezhneva, N., Nikitina, A., Ryzhkov, N. et al. Importance of buffering nanolayer position in Layer-by-Layer assembly on titania based hybrid photoactivity. J Sol-Gel Sci Technol 89, 92–100 (2019). https://doi.org/10.1007/s10971-018-4728-5
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