Layer-by-layer Films Research Articles

Layer-by-Layer Assembly and Electrochemical Study of Alizarin Red S-Based Thin Films.

Electroactive organic dyes incorporated in layer-by-layer (LbL) assemblies are of great interest for a variety of applications. In this paper, Alizarin Red S (ARS), an electroactive anthraquinone dye, is employed to construct LbL (BPEI/ARS)n films with branched poly(ethylene imine) (BPEI) as the complementary polymer. Unconventional LbL methods, including co-adsorption of ARS and poly(4-styrene sulfonate) (PSS) with BPEI to assemble (BPEI/(ARS+PSS))n, as well as pre-complexation of ARS with BPEI and further assembly with PSS to fabricate ((BPEI+ARS)/PSS)n, are designed for investigation and comparison. Film growth patterns, UV–Vis spectra and surface morphology of the three types of LbL assemblies are measured and compared to reveal the formation mechanism of the LbL films. Electrochemical properties including cyclic voltammetry and spectroelectrochemistry of (BPEI/ARS)120, (BPEI/(ARS+PSS))120 and ((BPEI+ARS)/PSS)120 films are studied, and the results show a slight color change due to the redox reaction of ARS. ((BPEI+ARS)/PSS)120 shows the best stability among the three samples. It is concluded that the manner of dye- incorporation has a great effect on the electrochemical properties of the resultant films.

New LbL‐TiO2/ZnO Compact Films to Improve Performance of Dye‐Sensitized Solar Cells

AbstractThe preparation of nanostructured thin films consisted of TiO2/ZnO bilayers (BL) and their application in dye‐sensitized solar cells (DSCs) are reported. The film was prepared by the Layer‐by‐Layer (LbL) technique using, respectively, acid and basic sols of TiO2 and ZnO nanoparticles. The particles in the sols were characterized by dynamic light scattering (DLS) and the compact morphology of the LbL films were probed by scanning electronic (SEM) and atomic force (AFM) microscopies. The photoelectrochemical parameters of DSCs with 0, 15 and 20 BL were assessed by current‐voltage (JxV) curves, incident photon‐to‐current efficiency (IPCE), electron lifetime and electrochemical impedance spectroscopy (EIS). These results revealed a significant improvement (up to 67%) on the DSC conversion efficiency promoted by LbL film underlayers, with enhancements ascribed to an efficient blocking effect preventing the FTO/I3− charge recombination and improved contact between the mesoporous‐TiO2 and the conducting substrate (FTO).

Layer-by-Layer Films of Graphene Nanoplatelets and Gold Nanoparticles for Methyl Parathion Sensing

The wide use of pesticides in agriculture makes necessary the development of cost-effective, easy, and rapid methods aiming for environmental and health protection. We propose the fabrication and investigation of layer-by-layer (LbL) films composed of reduced graphene oxide stabilized in polyelectrolytes in the presence and absence of gold nanoparticles (AuNPs) toward methyl parathion (MP) detection. In addition to the film assembly and sensing application, we performed a systematic investigation of the influence of MP distribution on the limit of detection and linear range of the sensor. Indium tin oxide (ITO) electrodes modified with the LbL films were applied by differential pulse voltammetry achieving an LOD and a linear range of 0.226 ppm and 0.25–40 ppm in the absence of AuNPs, while in the their presence, a wider linear range was achieved (0.5–60 ppm, with LOD of 0.770 ppm). Real sample analysis indicated potential application in water, ground, and vegetables, with recovery varying from 92% to 113%.

Dendrimer-grafted bioreducible polycation/DNA multilayered films with low cytotoxicity and high transfection ability

Controlled release of incorporated foreign DNA from multilayered films plays an important role in surface-mediated gene delivery. Herein, multilayered polyelectrolyte complex thin films, composed of dendrimer-grafted bio-reducible cationic poly(disulfide amine) and plasmid DNA, were fabricated via layer-by-layer (LBL) assembly for in vitro localized gene delivery. The UV absorbance and thickness of the LBL films were found to have linear correlation with the numbers of poly(disulfide amine)/DNA bilayers. Although LBL films were stable in PBS buffer, their degradation could be triggered by reducing agents (i.e. glutathione, GSH). The degradation rate of the films is directly proportional to the GSH concentration, which in turn affected the corresponding gene expression. All poly(disulfide amine)/DNA films exhibited lower cytotoxicity and higher transfection activity in comparison with PEI/DNA multilayered films. Moreover, LBL films showed the highest transfection efficiency in the presence of 2.5 mM GSH when cultured with 293T cells, with ~36% GFP-positive 293T cells after 5-days of co-culture. These DNA-containing reducible films could potentially be useful in gene therapy and tissue engineering by controlling the release of incorporated DNA.

Corrosion and Micro-abrasive Wear Behaviour of 2524-T3 Aluminium Alloy with PAni-NPs/PSS LbL Coating

In this paper, we present an alternative method to obtain thin films for coating protection on the surface of the AA2524-T3 Al-alloy by using the Layer-by-Layer (LbL) technique. The LbL films were fabricated by alternated immersion of the Al-alloy into a poly(styrene sulfonate) (PSS) and polyaniline nanoparticles (PAni-NPs) solutions, obtaining a PAni-NPs/PSS bilayer architecture. The LbL films were characterized by ultraviolet-visible spectroscopy (UV-Vis), Fourier-transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), electrochemical and micro-abrasive wear tests. The results show that the number of bilayers promotes shifts to less negative potentials, indicating an optimized system, in which the best performance was observed for a 15-bilayer PAni/PSS LbL film. The pitting potential (Epit) values shifted 130 mV (from -610 mV to -480 mV) in comparing a bare Al-alloy. The predominantly wear mechanism for AA2524-T3 with PAni-NPs/PSS bilayers was scratching whereas for the bare material there was an equivalence between scratching and rolling mechanisms. The results proved that the incorporation of PAni-NPS by the LbL method may be propitious as protective coating against corrosion in AA2524-T3 alloy.

Mechanically strong and electrically conductive multilayer MXene nanocomposites.

Polymer nanocomposites offer the opportunity to bridge properties of nanomaterials to the macroscale. In this work, layer-by-layer (LbL) assembly is used to demonstrate nanocomposites of 2D titanium carbide nanosheets (MXene) and clay nanoplatelets (montmorillonite) to fabricate freestanding thin films with unique multifunctional properties. These thin films can be tuned by adjusting the thickness to exhibit a tensile strength of 138 MPa-225 MPa, EMI specific shielding effectiveness normalized to thickness and density up to 24 550 dB cm2 g-1, and sheet resistance from 855 Ω sq-1-3.27 kΩ sq-1 (corresponding to a range of conductivity from 53 S m-1 to 125 S m-1). This composite is the strongest MXene-based LbL film prepared to date, in part due to the nacre-like brick-and-mortar structure. Ultra-strong, multifunctional films of this nature are desirable for many applications ranging from membranes, to structural and multifunctional composites, energy harvesting and storage, and materials for aerospace.

Flexible self-assembled polyelectrolyte thin films based on conjugated polymer: Quartz cristal microbalance dissipation (QCM-D) and cyclic voltammetry analysis

The fabrication of LbL (layer by layer) self-assembled thin films is attracting attention for various applications. Hence, the detailed characterization of these films is very vital. In this study, interaction between the conjugate/non-conjugated polyelectrolyte pairs, final film compositions and viscoelastic behavior of the LbL multilayer thin films are determined using the quartz crystal microbalance dissipation (QCM-D) technique. Firstly, anodic color changing polyaniline (PAni) based LbL films as electrodes are coated on flexible PET-ITO substrate and extensive characterizations are performed. Secondly, electrochemical characterization of these films in LiClO4/PC electrolyte is carried out. It is found from QCM-D and UV–vis analyzes that the films can be successfully coated on PET-ITO surface. Film thicknesses of (PAni/PAA)10, (PAni/PAA)20 and (PAni/PAA)40 films are determined from SEM images and they are found to be approximately 160, 240 and 410 nm, respectively. Ra roughness values of the same films are determined to be 6.56, 14.4 and 13.7 nm from AFM analysis. Also, cyclic voltammetry (CV) analysis reveals a significant reduction and oxidation peaks of the electroactive polymer. It is observed that (PAni/PAA)20 LbL film efficiently changed blue/green to light yellow/transparent color in LiClO4/PC liquid electrolyte over the potential range from −0.1 to 0.5 V vs Ag wire.

A transport model and constitutive equation for oppositely charged polyelectrolyte mixtures with application to layer-by-layer assembly.

We develop a general framework for transport of polyions, solvent and salt, with intended application to Layer-by-Layer (LbL) assembly of polyelectrolyte monolayers (PEMs). The formulation for the first time includes electrostatics, chemical potential gradients, and mechanical stress gradients as driving forces for mass transport. The general model allows all species to be mobile throughout the process and avoids the assumptions of stepwise instantaneous equilibrium and/or immobilized structures typical of previous approaches, while reducing to these models in appropriate limits. A simple constitutive equation is derived for a mixture of oppositely charged polyelectrolytes that accounts for network strand dilution and cross-chain ion pairing by appending reactive terms to the Smoluchowski probability diffusion equation for network strand end-to-end vectors. The resulting general framework encompasses the Poisson equation describing the electrostatic potential distribution, an osmotic pressure balance, a stress constitutive equation, and a generalized flux law of polymer transport. The computational domain is split into a PEM phase and an external solution phase with an appropriate boundary condition derived for the interface between the two. The mobile species (water and small salt ions) are taken to be in a state of dynamic equilibrium with their distributions enslaved to the perturbations in the two polyion compositions. The proposed model captures the swelling response of PEM films to external solutions. For the first time, we studied the effects of the temporal evolution of electrostatic and stress distribution on the rate of chain loss and absorption during rinsing and dipping of an idealized and arbitrarily selected and rigid brush layer into external solutions. The temporal evolution provides a kinetic basis for the ability of LbL films to grow under conditions that thermodynamics alone suggests would cause them to be washed away and to account for partial desorption during washing. The proposed transport framework constitutes a solid basis for eventual quantitative modeling of LbL assembly and transport in polyion networks more generally.

Functional Surfaces through Controlled Assemblies of Upper Critical Solution Temperature Block and Star Copolymers.

Endowing surfaces with multiple advanced functionalities, such as temperature-controlled swelling or the triggered release of functional small molecules, is attractive for a large variety of applications ranging from smart textiles to advanced biomedical applications. This Invited Feature Article summarizes recent advances in the development of upper critical solution temperature (UCST) behavior of copolymers in aqueous solutions and compares the fundamental differences between lower critical solution temperature (LCST) and UCST transitions. The effect of polymer chemistry and architecture on UCST transitions is discussed for block copolymer micelles (BCMs) and star polymers in solution and assembled at surfaces. The inclusion of such nanocontainers (i.e., BCMs and star polymers) in layer-by-layer (LbL) coatings and how to control their responsive behavior through deposition conditions and binding partners is explored. Finally, the inclusion and temperature-triggered release of functional small molecules is explored for nanocontainers in LbL coatings. Taken together, UCST nanocontainers containing LbL films are promising building blocks for the development of new generations of practical, functional surface coatings.

Antibacterial layer-by-layer coatings to control drug release from soft contact lenses material

In this study we investigated the possibility of using polyelectrolytes with antibacterial properties to form layer-by-layer (LbL) coatings on contact lens materials with the objective of controlling the release of ophthalmic drugs, while minimizing bacterial growth. A silicone-based hydrogel recently proposed by our group was chosen as a drug releasing soft contact lens (SCL) material and three drugs were tested: moxifloxacin hydrochloride (MXF), chlorhexidine diacetate monohydrate (CHX), and diclofenac sodium salt (DIC). Employed coatings involved combinations of sodium alginate (ALG), chitosan (CHI), sodium hyaluronate (HA) and polylysine hydrobromide (PLL), using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) as a cross-linking agent. Controlled release of DIC was achieved using two double layers of the following combinations: ALG/PLL (EDC), HA (EDC)/CHI and HA/PLL (EDC) + Drug. Furthermore, the physical properties of the coated lens material were kept, or even improved, and bacterial growth was reduced. In contrast, these coatings did not retard the release of MXF and CHX. The specificity of the barrier effect of these LbL films for DIC may be attributed to the formation of reversible interactions between DIC and the polyelectrolyte chains. A top layer of HA was needed to reduce the interaction with tear proteins. The in vivo efficacy of a contact lens coated with ALG/PLL (EDC)//HA and loaded with DIC was predicted using a simplified mathematical model to estimate the drug concentration in the tear fluid. The period of time during which the estimated concentration of DIC remained above the half-maximum inhibitory concentrations for the active enzymes in the process of inflammation, was at least double that obtained with the uncoated sample.

Higher cellular interaction and faster production of natural rubber latex LbL films by spraying method

Natural rubber latex (NRL) from Hevea brasiliensis can accelerate wound healing, but membranes made of NRL have shown low cellular interaction limiting their application as implants. By employing dipping layer-by-layer (LbL) technique, we were previously able to glow human fibroblast cells on NRL films. But this method is time consuming which hinders industrialization. Therefore, NRL films were produced using polyethyleneimine (PEI) by spraying (sp) LbL method, which proved to be 10 times faster than dipping techniques. Rinsed and non-rinsed sp films were produced by triggering the spray devices five times for each material. Both (PEI/NRL)5 and (PEI/NRL)15 spraying and dipping films were then analyzed by UV-vis, AFM, and contact angle measurements. In order to evaluate the cellular interaction, Vero cells were directly cultivated on the LbL films up to 24 h. Results showed that despite non-rinsed sp films having lower amount of material than dipping ones, Vero cells adhere similarly on both. Rinsed (PEI/NRL)5 sp films, on the other hand, presented higher amount of cellular attachment as well as smaller NRL particles on the films’ surface. Thus, it was possible to increase cellular interaction of NRL and produce films 10 times faster by employing spraying LbL method.

Oxidative Layer-By-Layer Multilayers Based on Metal Coordination: Influence of Intervening Graphene Oxide Layers.

Layer-by-layer (LbL) fabricated oxidative multilayers consisting of successive layers of inorganic polyphosphate (PP) and Ce(IV) can electrolessly form thin conducting polymer films on their surface. We describe the effect of substituting every second PP layer in the (PP/Ce) multilayers for graphene oxide (GO) as a means of modifying the structure and mechanical properties of these (GO/Ce/PP/Ce) films and enhancing their growth. Both types of LbL films are based on reversible coordinative bonding between the metal ions and the oxygen-bearing groups in PP and GO, instead of purely electrostatic interactions. The GO incorporation leads to the doubling of the areal mass density and to a dry film thickness close to 300 nm after 4 (GO/Ce/PP/Ce) tetralayers. The film roughness increases significantly with thickness. The (PP/Ce) films are soft materials with approximately equal shear storage and loss moduli, but the incorporation of GO doubles the storage modulus. PP displays a marked terminating layer effect and practically eliminates mechanical losses, making the (GO/Ce/PP/Ce) films almost pure soft elastomers. The smoothness of the (PP/Ce) films and the PP-termination effects are attributed to the reversible coordinative bonding. The (GO/Ce/PP/Ce) films oxidize pyrrole and 3,4-ethylenedioxythiophene (EDOT) and form polypyrrole and PEDOT films on their surfaces. These polymer films are considerably thicker than those formed using the (PP/Ce) multilayers with the same nominal amount of cerium layers. The GO sheets interfere with the polymerization reaction and make its kinetics biphasic. The (GO/Ce) multilayers without PP are brittle and thin.

Synthetic Charge-Invertible Polymer for Rapid and Complete Implantation of Layer-by-Layer Microneedle Drug Films for Enhanced Transdermal Vaccination.

The utility of layer-by-layer (LbL) coated microneedle (MN) skin patches for transdermal drug delivery has proven to be a promising approach, with advantages over hypodermal injection due to painless and easy self-administration. However, the long epidermal application time required for drug implantation by existing LbL MN strategies (15-90 min) can lead to potential medication noncompliance. Here, we developed a MN platform to shorten the application time in MN therapies based on a synthetic pH-induced charge-invertible polymer poly(2-(diisopropylamino) ethyl methacrylate- b-methacrylic acid) (PDM), requiring only 1 min skin insertion time to implant LbL films in vivo. Following MN-mediated delivery of 0.5 μg model antigen chicken ovalbumin (OVA) in the skin of mice, this system achieved sustained release over 3 days and led to an elevated immune response as demonstrated by significantly higher humoral immunity compared with OVA administration via conventional routes (subcutaneously and intramuscularly). Moreover, in an ex vivo experiment on human skin, we achieved efficient immune activation through MN-delivered LbL films, demonstrated by a rapid uptake of vaccine adjuvants by the antigen presenting cells. These features, rapid administration and the ability to elicit a robust immune response, can potentially enable a broad application of microneedle-based vaccination technologies.

Layer-by-layer DNA films incorporating highly transfecting bioreducible poly(amido amine) and polyethylenimine for sequential gene delivery

BackgroundThe layer-by-layer (LbL) assembly method offers a molecular level control of the amount and spatial distribution of bioactive molecules. However, successful clinical translation of LbL film technology will most certainly require a better understanding and control of not only the film assembly process, but also film disassembly kinetics in physiologic conditions.PurposeThis work focuses on the understanding and control of degradation properties of LbL films for localized gene delivery.MethodsBioreducible poly(amido amine)s (PAAs) containing cystaminebisacrylamide (CBA), methylenebisacrylamide, and 5-amino-1-pentanol (APOL) were synthesized by Michael addition polymerization for the construction of bioreducible LbL films capable of sequential gene delivery.ResultsThe synthesized PAAs were screened for desirable buffering capacity, cell transfection, and cytotoxicity characteristics together with 25 kDa branched polyethylenimine (PEI) and cross-linked 800 Da PEI. By screening the various polycations we were able to identify a copolymer of CBA and APOL for the subsequent construction of the LbL films. By incorporating a highly transfecting polycation and a nondiffusing polycation we were able to improve the overall transfection of HEK293 and MC3T3 cells from the bioreducible LbL films. We also demonstrated the dual-stage release and transfection of two different DNAs from the LbL films.ConclusionThe results indicate that LbL films consisting of bioreducible PAAs and non-diffusing polyelectrolytes have excellent degradation properties for the development of LbL coating technology for localized gene delivery applications.

Preparation of multilayer films using the negative charge of phenylboronic acid and its response to pH change, fructose, and hydrogen peroxide

Functional layer-by-layer (LbL) multilayer films using phenylboronic acid (PBA) have been typically prepared by exploiting the boronate ester bond between PBA and a diol polymer as the driving force. However, we have prepared PBA-containing LbL films through the electrostatic interaction of PBA and polycations, Poly(acrylamide-ran-3-acrylamidephenylboronic acid) (PBA-PAA) and various polycations such as poly(allylamine) hydrochloride (PAH), poly(ethyleneimine) (PEI), poly(diallyldimethylammonium chloride) (PDDA), and polyamidoamine (PAMAM) dendrimer were used. Construction of the multilayer films was influenced by the modification ratio of PBA, the shape of the polycations, solution pH, and the ion concentration. The results showed that the multilayered film was formed by electrostatic interaction. A multilayer film prepared from 10% PBA containing PBA-PAA and PAH showed pH, fructose, and H2O2 responses because these stimuli disturbed the charge balance inside the multilayer films. Such decomposition responses were comparable to that of PBA multilayer films constructed using boronate ester bonds.

Ethanol Measurement Using Hetero-Core Structured Optical Fiber Covered with Layer-By-Layer Thin Film.

Ethanol measurements are performed in an ethanol/water solution utilizing an ethanol sensor based on a hetero-core structured optical fiber covered with a layer-by-layer thin film. The layer-by-layer (LbL) thin film was prepared using poly (allylamine hydrochloride) and poly styrene sulfonate. When the sensor was immersed in water, the propagating light intensity decreased with increasing ethanol concentration. This behavior suggested that the LbL film contracted due to the presence of ethanol, and the refractive index of the film increased, resulting in increasing propagating light leaks at the hetero-core of the fiber. The ethanol sensor was applied to a variety of spirits, and the propagating light intensity decreased with increasing ethanol concentration.

Preparation of Nafion/Polycation Layer-by-Layer Films for Adsorption and Release of Insulin.

Thin films were prepared using layer-by-layer (LbL) deposition of Nafion (NAF) and polycations such as poly(allylamine hydrochloride) (PAH), poly(ethyleneimine) (PEI), and poly(diallydimethylammonium chloride) (PDDA). Insulin was then adsorbed on the NAF-polycation LbL films by immersion in an insulin solution. The NAF-polycation LbL films were characterized using a quartz crystal microbalance and an atomic force microscope. The release of insulin from the LbL films was characterized using UV-visible adsorption spectroscopy and fluorescence emission spectroscopy. The greatest amount of insulin was adsorbed on the NAF-PAH LbL film. The amount of insulin adsorbed on the (NAF/PAH)5NAF LbL films by immersion in a 1 mg mL−1 insulin solution at pH 7.4 was 61.8 µg cm−2. The amount of insulin released from the LbL films was higher when immersed in insulin solutions at pH 2.0 and pH 9.0 than at pH 7.4. Therefore, NAF-polycations could be employed as insulin delivery LbL films under mild conditions and as an insulin release control system according to pH change.

Graphene Oxide-Assisted Accumulation and Layer-by-Layer Assembly of Antibacterial Peptide for Sustained Release Applications.

Fabrication of antibacterial materials with sustained release of active components is of great importance for long-term antibacterial applications. Graphene oxide (GO) has been found to be an excellent carrier for accumulating the antibacterial peptide of G(IIKK)4I-NH2 and mediating its loading into the layer-by-layer (LBL) films for sustained release applications. G(IIKK)4I-NH2 takes random coiled conformation in monomeric state below 0.17 mM but self-assembles into supramolecular aggregates with α-helical secondary structure at higher concentrations. It can bind onto GO surface in both monomeric and aggregate states to form stable GO@G(IIKK)4I-NH2 composites. Upon binding, the local amphiphilic environment of GO surface induces a conformational transition of G(IIKK)4I-NH2 monomers from random coils to α-helix. The aggregate binding enhances the loading amount greatly. GO (1 mg) can load as high as 1.7 mg of peptide at saturation. This enables the GO@G(IIKK)4I-NH2 composites to serve as reservoirs for sustained release of active G(IIKK)4I-NH2 monomers. Moreover, G(IIKK)4I-NH2 itself shows low efficiency in LBL assembly, whereas the GO@G(IIKK)4I-NH2 composites are ideal LBL assembling units with highly enhanced loading efficiency of G(IIKK)4I-NH2. The LBL films involving degradable poly(β-amino esters) can realize sustained release of G(IIKK)4I-NH2 for bacteria killing in a well-controlled manner. This study demonstrates an efficient strategy for fabrication of long-durable antibacterial materials and surface coatings by using GO as the carrier for drug accumulation and loading.

Photocatalytic properties of layer-by-layer thin films of hexaniobate nanoscrolls

High efficient photocatalytic surfaces were obtained through the layer-by-layer (LbL) deposition of hexaniobate nanoscrolls on conductive glasses. These films were deposited by alternative immersions of the substrate into exfoliated hexaniobated suspensions (pH = 8) and poly(allylamine hydrochloride) solutions (pH = 4). The organic species were further removed by thermal treatment leading to a fuzzy assembly of hexaniobate nanoscrolls. Pre-adsorption of [Pt(NH3)4]2+ cations on the niobate layers allows the production of metallic Pt nanoclusters on the film layers. The Pt-modified films exhibited apparent quantum yields of (4.0 ± 0.5) % for H2 evolution from water/methanol mixtures under UV-A irraditation. The H2 evolution rates varied linearly with the number of deposited bilayers, indicating that no active sites are lost as the film is grown. The photoelectrochemical properties of the films reveal that the small size of the hole scavenger and its easy diffusion into the hexaniobate layers are key aspects for the photocatalytic activity. In the absence of alcohols as hole scavengers, irradiation of the hexaniobate LbL films in aqueous solutions leads to the production of surface-bound peroxides that limit the photocatalytic water splitting ability of these materials. The results presented here provide evidence for the effectiveness of the LbL technique to deposit thin films of layered materials retaining their interesting adsorption chemistry. This methodology can be further employed for the development of highly active photocatalytic surfaces.

Sol gel synthesis of 3-n-propyl(4-aminomethyl)pyridinium silsesquioxane chloride and the enhanced electrocatalytic activity of LbL films

A silsesquioxane based on a silica matrix and 4-(aminomethyl)pyridine group was successfully synthesized using the sol–gel process with the proposal of two different carbonic chain arrangments in the structure of the silica polymer, observed employing NMR techniques. The silsesquioxane proposed succeeds an improvement of the adsorption of monomer electroactive species on the surface of the electrode obtained through films assembly, this fact was attributed to the presence of two coordinating nitrogen in new silsesquioxane. In this study, the Layer-by-Layer (LbL) technique was shown suitable to be used to produce electroactive electrodes with indium tin oxide electrode (ITO) coated by tetrasulfonated nickel phthalocyanine (NiTsPc) alternated with the silsesquioxane. Voltammetric techniques were used to investigate the electrochemical behavior of the nitrite oxidation, which exhibited an enhanced current response at the modified electrode. The proposed electroddisplayed a current response which varied linearly with the concentration of nitrite in the range 0.113 to 0.860 mmol L−1 with a detection limit of 0.026 mmol L−1, a sensitivity of 32.06 µA (mmol L−1) and relative standard deviation of approximately 3%.