pH-Dependence Cytotoxicity Evaluation of Artepillin C against Tumor Cells.

Brazilian green propolis is a well-known product that is consumed globally. Its major component, Artepillin C, showed potential as an antitumor product. This study explored the impact of Artepillin C on fibroblast and glioblastoma cell lines, used as healthy and very aggressive tumor cell lines, respectively. The focus of the study was to evaluate the pH-dependence of Artepillin C cytotoxicity, since tumor cells are known to have a more acidic extracellular microenvironment compared to healthy cells, and Artepillin C was shown to become more lipophilic at lower pH values. Investigations into the pH-dependency of Artepillin C (6.0-7.4), through viability assays and live cell imaging, revealed compelling insights. At pH 6.0, MTT assays showed the pronounced cytotoxic effects of Artepillin C, yielding a notable reduction in cell viability to less than 12% among glioblastoma cells following a 24 h exposure to 100 µM of Artepillin C. Concurrently, LDH assays indicated significant membrane damage, affecting approximately 50% of the total cells under the same conditions. Our Laurdan GP analysis suggests that Artepillin C induces autophagy, and notably, provokes a lipid membrane packing effect, contributing to cell death. These combined results affirm the selective cytotoxicity of Artepillin C within the acidic tumor microenvironment, emphasizing its potential as an effective antitumor agent. Furthermore, our findings suggest that Artepillin C holds promise for potential applications in the realm of anticancer therapies given its pH-dependence cytotoxicity.

Influence of solvents on the morphology of Langmuir and Langmuir-Schaefer films of PCBM and PCBM-based oligomers and polymers.

Fullerene-based polymers and oligomers combined with non-fullerene acceptors show extremely high efficiencies in organic photovoltaic devices. Furthermore, fullerene-based materials are of interest for use in anti-cancer and anti-viral treatments, where their presence can enhance the efficacy of medication considerably. Therefore, it remains important to understand their morphology and electronic properties to improve devices and technological applications. The main goal of this study is to prepare and characterize Langmuir and Langmuir-Schaefer films of PCBM-based materials to investigate the influence of different solvents such as chloroform, toluene, and xylene, and co-components on their morphology. PCBM-based materials were thus studied either alone or in mixtures with a polythiophene derivative (poly(3-hexythiophene), P3HT) commonly used in organic photovoltaic devices. The formation of Langmuir films was studied using surface pressure isotherms and Brewster's angle microscopy (BAM), where the homogeneity, phase behavior, and morphology of the films were investigated. In addition, Langmuir-Schaefer films were characterized by UV-visible absorption spectroscopy, atomic force microscopy (AFM), and Raman spectroscopy, providing information on the morphology of the solid films. This study has shown that it is possible to successfully fabricate Langmuir and Langmuir-Schaefer films of PCBM and PCBM-based oligomers and polymers, both pure and in mixtures with P3HT, to compare their organization, roughness, and optical properties. With the Langmuir films, it was possible to estimate the area of the molecules and visualize their aggregation through BAM images, establishing a relationship between the area occupied by these materials and the solvent used. All characterization techniques corroborate that the use of chloroform significantly reduced the roughness of the LS films mixed with P3HT and also presented a higher ordering compared to films prepared with xylene solutions.

Immunoassay platform with surface-enhanced resonance Raman scattering for detecting trace levels of SARS-CoV-2 spike protein.

The early diagnosis of Coronavirus disease (COVID-19) requires either an accurate detection of genetic material or a sensitive detection of viral proteins. In this work, we designed an immunoassay platform for detecting trace levels of SARS-CoV-2 spike (S) protein. It is based on surface-enhanced resonance Raman scattering (SERRS) of methylene blue (MB) adsorbed onto spherical gold nanoparticles (AuNPs) and coated with a 6 nm silica shell. The latter shell in the SERRS nanoprobe prevented aggregation and permitted functionalization with SARS-CoV-2 antibodies. Specificity of the immunoassay was achieved by combining this functionalization with antibody immobilization on the cover slides that served as the platform support. Different concentrations of SARS-CoV-2 antigen could be distinguished and the lack of influence of interferents was confirmed by treating SERRS data with the multidimensional projection technique Sammon's mapping. With SERRS using a laser line at 633 nm, the lowest concentration of spike protein detected was 10 pg/mL, achieving a limit of detection (LOD) of 0.046 ng/mL (0.60 pM). This value is comparable to the lowest concentrations in the plasma of COVID-19 patients at the onset of symptoms, thus indicating that the SERRS immunoassay platform may be employed for early diagnosis.

Titanium-Based Alloy Surface Modification with TiO2 and Poly(sodium 4-styrenesulfonate) Multilayers for Dental Implants.

Implant placement is an important repair method in dentistry and orthopedics. Increasing efforts have focused on optimizing the biocompatibility and osseointegration properties of titanium (Ti) and Ti-based alloys. In this work, Ti-based alloys were modified by the layer-by-layer (LbL) technique, which is a simple and versatile method for surface modification. The morphology and chemical structure of LbL films of poly(sodium 4-styrenesulfonate) (PSS) and Ti dioxide (TiO2) nanoparticles were first characterized employing ultraviolet-visible and Fourier-transform infrared spectroscopies as well as atomic force microscopy for further application in Ti-based alloy implants. The changes provoked by the LbL PSS/TiO2 film on the Ti-based alloy surfaces were then investigated by scanning electron microscopy and micro-Raman techniques. Finally, in vivo tests (immunolabeling and biomechanical analysis) performed with screw implants in rats suggested that PSS/TiO2 multilayers promote changes in both topography and chemical surface properties of the screw, providing beneficial effects for osteoblast activity. This simple and relatively low-cost growth process can open up possibilities to improve dental implants and, probably, bone implants in general.

Supramolecular architecture and electrical conductivity in organic semiconducting thin films.

Organic thin films are an essential component of the structure of optical and electronic devices. However, the optical and electrical properties of these films depend on their supramolecular architecture, which may vary according to the techniques used to manufacture them. Here, the correlation between conductivity and supramolecular architecture was investigated. The supramolecular architecture was analyzed in terms of the molecular organization and J- or H-aggregation established during the fabrication of perylene tetracarboxylic diimide (PTCD) nanometric films. Three deposition techniques, Langmuir-Schaefer (LS), Langmuir-Blodgett (LB), and Physical Vapor Deposition (PVD), were evaluated. The UV-vis absorption spectra indicated that LS, LB, and PVD films grow homogeneously. Also, the presence of J and H aggregates was observed for all films, the H aggregates prevailing for the LB film. The FTIR measurements suggested that the molecular organization is similar for LS and LB films, with a tendency to form head-on organization onto a solid substrate. For the PVD film, the perylene macrocycles are inclined approximately 45° relative to the substrate. AFM measurements indicated a homogenous surface for all films. In terms of electrical conductivity, the highest conductivity was found for LS, followed by LB and PVD. The conductivity values were interpreted in terms of molecular organization and J- or H-aggregate formation.

Correlating Artepillin C cytotoxic activity on HEp-2 cells with bioinspired systems of plasma membranes.

Artepillin C is the main compound present in propolis from Baccharis dracunculifolia, whose antitumor activity has been the focus of many studies. Herein, we shall investigate the Artepillin C mechanisms of action against cells derived from the oropharyngeal carcinoma (HEp-2). Cytotoxicity tests revealed that the concentrations of Artepillin C required to reduce cell viability by 50% (CC50) are dependent on the incubation time, decreasing from 40.7 × 10-5 mol/L to 15.7 × 10-5 mol/L and 9.05 × 10-5 mol/L considering 12, 24 and 48 h, respectively. Hydrophobic interactions on neutral species of Artepillin C induce aggregation over the HEp-2 plasma membrane, given the acid conditions of the cellular culture. Indeed, Langmuir monolayers mimicking cellular membranes of tumor cells revealed Artepillin C affinity to interact with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) containing 20 mol% of 1,2-dipalmitoyl-sn-glychero-3-phosphoserine (DPPS), leading aggregation on giant unilamellar vesicles (GUVs) at pH 3.2. Moreover, leakage experiments on GUVs have shown that the presence of DPPS enhances the efflux of the fluorescent probe signaling the membrane permeabilization, which is the origin of the necrotic pathway triggered in HEp-2 cells, as observed by flow cytometry assays.

Understanding the langmuir and Langmuir-Schaefer film conformation of low-bandgap polymers and their bulk heterojunctions with PCBM.

Low-bandgap polymers are widely used as p-type components in photoactive layers of organic solar cells, due to their ability to capture a large portion of the solar spectrum. The comprehension of their supramolecular assembly is crucial in achieving high-performance organic electronic devices. Here we synthezed two exemplar low-bandgap cyclopentadithiophene (CPDT):diketopyrrolopyrrole (DPP)-based polymers, with either a twelve carbon (C12) or a tri etyleneglycol (TEG) side chains on the DPP units (respectively denoted PCPDTDPP_C12 and PCPDTDPP_TEG). We deposited Langmuir-Schaefer films of these polymers blended with the widely used electron donor material [6,6]-phenyl-C61-butyric-acid methyl ester (PCBM). We then characterized the conformational, optical and morphological properties of these films. From the monolayers to the solid films, we observed distinct self-organization and surface properties for each polymer due to the distinct nature of their side chains. Emphasizing their attraction interactions with PCBM and the phase transitions according to the surface pressure. The elements amount on the surface, calculated through the XPS, gave us a good insight on the polymers' conformations. Through UV-visible absorption spectroscopy, the improvement in the PCPDTDPP film ordering upon PCBM addition is evident and we saw the contribution of the polymer units on the optical response. Chemical attributions of the polymers were assigned using FTIR Spectroscopy and Raman Scattering, revealing the physical interaction after mixing the materials. We showed that it is possible to build nanostructured PCPDTDPPs films with a high control of their molecular properties through an understanding of their self-assembly and interactions with an n-type material.

Vibrational Spectroscopic Characterization and Coherent Anti-Stokes Raman Spectroscopy (CARS) Imaging of Artepillin C.

In the following work, the vibrational spectroscopic characteristics of artepillin C are reported by means of Fourier transform infrared (FT-IR) and Raman spectroscopies, surface-enhanced Raman scattering (SERS), and coherent anti-Stokes Raman scattering (CARS) microscopy. Artepillin C is an interesting compound due to its pharmacological properties, including antitumor activity. It is found as the major component of Brazilian green propolis, a resinous mixture produced by bees to protect their hives against intruders. Vibrational spectroscopic techniques have shown a strong peak at 1599 cm-1, assigned to C=C stretching vibrations from the aromatic ring of artepillin C. From these data, direct visualization of artepillin C could be assessed by means of CARS microscopy, showing differences in the film hydration obtained for its neutral and deprotonated states. Raman-based methods show potential to visualize the uptake and action of artepillin C in biological systems, triggering its interaction with biological systems that are needed to understand its mechanism of action.

The pesticide picloram affects biomembrane models made with Langmuir monolayers.

Cell membrane models are useful to obtain molecular-level information on the interaction of biologically-relevant molecules such as pesticides whose activity is believed to depend on its effects on the membrane. In this study, we investigated the interaction between the widely used pesticide picloram with Langmuir monolayers of binary and ternary mixtures comprising 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), sphingomyelin (SM) and cholesterol (Chol), which could be taken as representative of ocular membranes in humans. Picloram expanded the molecular area of DOPC/SM and DOPC/SM/Chol monolayers as the pesticide penetrated the hydrophobic region of the mixtures. A clear correlation was also found between the compressibility modulus (Cs-1) and the presence of cholesterol in the ternary monolayer. Data from polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS) confirmed that picloram interacts with both the acyl chains and headgroups. Spectral shifts and band broadening were induced by picloram, particularly for the phosphate and choline groups, probably owing to its H-bonding ability. The effects reported here on the lipid monolayers may be evidence of the possible activity of picloram on mammalian cell membranes, which highlights the importance of strict control of the level of exposure of humans dealing with pesticides.

Disruption of giant unilamellar vesicles mimicking cell membranes induced by the pesticides glyphosate and picloram.

Giant unilamellar vesicles (GUVs) have been one of the most extensively investigated membrane model to study cell membrane-ligand interactions. In this study, we investigated the interaction between glyphosate and picloram with GUVs made with sphingomyelin (SM), cholesterol (CHOL), and dioleoyl-sn-glycerol-3-phosphocholine (DOPC) (DOPC/SM (1:1), DOPC/CHOL/SM (1:1:1)) in a physiological environment using confocal and phase contrast microscopy. At high pesticide concentrations (70 to 90 µM), we generally found the GUVs undergoing a physical such as contouring, elongation, and eventually lose their characteristic spherical shape. In addition, to determine the comparative effect of the pesticides, control experiments were performed using GUVs made with only DOPC and DOPC/SM 1:1. The results show that, at low concentration (0.5 µM), a significant effect was observed during a 30 min incubation time. These findings also suggest that cholesterol may play a significant role in the permeability of the vesicle against the action of the pesticides, which have important biological implications on the lipid composition of the membrane.

Interactions of Lipid Polar Headgroups with Carbendazim Fungicide.

Carbendazim (MBC) is a fungicide widely used in agriculture which allows the high productivity of several cultures, a necessary condition considering the growing of the world population. Moreover, MBC has environmental impact mainly on the soil and water sources, and consequently, on animal and human lives. However, even though the toxicity of fungicides is well established, their action mechanism in cell membranes are not completely understood. Herein, we investigate the interaction of different polar headgroups: dimethyldioctadecylammonium bromide (DODAB), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (DPPG); and different chain unsaturation degrees DPPC, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) with MBC. Lipid monolayers at the air/water interface were applied as mimetic systems of cell membranes to investigate the interaction with MBC dissolved in the ultrapure water subphase. It was found that the interaction is driven preferably by electrostatic forces of the headgroups, with higher affinity for DODAB (cationic), intermediate for DPPC (zwitterionic), and absent for DPPG (anionic), considering the monolayer in the condensed phase. DODAB-MBC electrostatic interaction was consistent with FTIR (cast films). We also investigated giant unilamellar vesicles (GUVs) of zwitterionic lipids (DPPC, POPC, and DOPC) with distinct chain unsaturations in the presence of MBC by confocal microscopy and molecular dynamic (MD) simulations. The results indicate that, unlike the chain unsaturation, the polar headgroups play key role on the lipid-MBC interaction.

Surface Plasmon Resonances in Silver Nanostars.

The recent development of silver nanostars (Ag-NSs) is promising for improved surface-enhanced sensing and spectroscopy, which may be further exploited if the mechanisms behind the excitation of localized surface plasmon resonances (LSPRs) are identified. Here, we show that LSPRs in Ag-NSs can be obtained with finite-difference time-domain (FDTD) calculations by considering the nanostars as combination of crossed nanorods (Ag-NRs). In particular, we demonstrate that an apparent tail at large wavelengths ( λ ≳ 700 nm) observed in the extinction spectra of Ag-NSs is due to a strong dipolar plasmon resonance, with no need to invoke heterogeneity (different number of arms) effects as is normally done in the literature. Our description also indicates a way to tune the strongest LSPR at desired wavelengths, which is useful for sensing applications.

New trends in plasmonic (bio)sensing.

The strong enhancement and localization of electromagnetic field in plasmonic systems have found applications in many areas, which include sensing and biosensing. In this paper, an overview will be provided of the use of plasmonic phenomena in sensors and biosensors with emphasis on two main topics. The first is related to possible ways to enhance the performance of sensors and biosensors based on surface plasmon resonance (SPR), where examples are given of functionalized magnetic nanoparticles, magnetoplasmonic effects and use of metamaterials for SPR sensing. The other topic is focused on surface-enhanced Raman scattering (SERS) for sensing, for which uniform, flexible, and reproducible SERS substrates have been produced. With such recent developments, there is the prospect of improving sensitivity and lowering the limit of detection in order to overcome the limitations inherent in ultrasensitive detection of chemical and biological analytes, especially at single molecule levels.

Supramolecular Arrangement of Iron Phthalocyanine in Langmuir-Schaefer and Electrodeposited Thin Films.

The supramolecular arrangement in thin film technology has been explored through different deposition techniques aiming to control the film properties at the molecular level. We report on the formation of iron phthalocyanine (FePc) films using both Langmuir-Schaefer (LS) and electrodeposition methods. The multilayer formation was monitored with ultraviolet-visible absorption spectroscopy (UV-vis) and electrochemical measurements. According to Raman spectroscopy, atomic force microscopy (AFM), and scanning electron microscopy (SEM), the surface morphology of electrodeposited films is more homogeneous than LS films at micro and nanometer scales. From FTIR spectroscopy, the FePc molecules in the electrodeposited films are oriented preferentially with the macrocycle parallel to the substrate surface (flat-on), while a slight tilt is suggested in LS films, being both films crystalline. Therefore, the use of different deposition techniques allowed the fabrication of thin films from FePc with distinct supramolecular arrangements, leading to distinct electrochemical properties. For instance, the electrodeposited films show higher surface coverage, suggesting a more compact structure, which favors the charge transfer and smaller energy gap. The possibility of tuning some properties according to deposition technique for the same material can help the development of technological applications such as electronic or sensing devices.

New trends in plasmonic (bio)sensing

Abstract The strong enhancement and localization of electromagnetic field in plasmonic systems have found applications in many areas, which include sensing and biosensing. In this paper, an overview will be provided of the use of plasmonic phenomena in sensors and biosensors with emphasis on two main topics. The first is related to possible ways to enhance the performance of sensors and biosensors based on surface plasmon resonance (SPR), where examples are given of functionalized magnetic nanoparticles, magnetoplasmonic effects and use of metamaterials for SPR sensing. The other topic is focused on surface-enhanced Raman scattering (SERS) for sensing, for which uniform, flexible, and reproducible SERS substrates have been produced. With such recent developments, there is the prospect of improving sensitivity and lowering the limit of detection in order to overcome the limitations inherent in ultrasensitive detection of chemical and biological analytes, especially at single molecule levels.

Interaction between 17 α-ethynylestradiol hormone with Langmuir monolayers: The role of charged headgroups.

The persistence of steroid hormones disposed of in the environment may pose risks to the health of humans and wildlife, which brings the need of understanding their mode of action, believed to occur in cell membranes. In this study, we investigate the molecular-level interactions between the synthetic hormone 17 α-ethynylestradiol (EE2) and Langmuir monolayers that represent simplified cell membranes. In surface pressure isotherms, EE2 was found to expand the monolayers at low surface pressures of the positively charged dimethyldioctadecylammonium bromide (DODAB), zwitterionic 1,2-dipalmitoyl-sn-glycerol-3-phosphocholine (DPPC), negatively charged 1,2-dipalmitoyl-sn-glycero-3-phosphoglycerol (DPPG), and partially anionized stearic acid (StAc). The largest effects were observed for the charged DODAB and DPPG. At the pressure (30mN.m-1) corresponding to the molecular packing of a cell membrane, EE2 caused the compressibility modulus to decrease, again with the largest changes occurring for DODAB and DPPG. The effects from EE2 on the packing of the lipid molecules at this high pressure depended essentially on the size of the headgroups, with EE2 contributing to the area per lipid for StAc and DODAB, whose headgroups are small. EE2 interacted with the headgroups of all lipids and StAc, also affecting the ordering of the tails for DODAB, DPPG and DPPC, according to in situ polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS). Based on the analysis with the two characterization methods, we propose a model for the EE2 positioning and molecular groups involved in the interaction, which should be relevant to unveil the endocrine disrupting action of EE2.

Sensitive detection of estriol hormone in creek water using a sensor platform based on carbon black and silver nanoparticles.

We report the electrochemical detection of estriol using carbon black nanoballs (CNB) decorated with silver nanoparticles (AgNP) as electrode material. Homogeneous, porous films on glassy carbon electrodes (GCE) were obtained, with diameters of 20 - 25nm for CNB and 5 - 6nm for AgNP. CNB/AgNP electrodes had increased conductivity and electroactive area in comparison with bare GCE and GCE/CNB, according to cyclic voltammetry and electrochemical impedance spectroscopy. The oxidation potential peak was also down shifted by 93mV, compared to the bare GC electrode. Differential pulse voltammetry data were obtained in 0.1molL-1 PBS (pH 7.0) to detect estriol without the purification step, in the linear range between 0.2 and 3.0µmolL-1 with detection and quantification limits of 0.16 and 0.5µmolL-1 (0.04 and 0.16mgL-1), respectively. The sensor was used to detect estriol in a creek water sample with the same performance as in the official methodology based on high performance liquid chromatography.

Influence of the Supramolecular Arrangement in the Electrical Conductivity of Poly(thiophene) Thin Films.

Thin films of regioregular polythiophene derivatives have had their optical, structural and morphological properties characterized, but there is still a lack of comparative studies to determine the effect from deposition techniques, especially on the electrical properties. In this study, we produced Langmuir-Schaefer and spin-coated films of regioregular alkyl-substituted polythiophene derivatives (P3AT) to investigate how distinct supramolecular arrangements can affect their properties. The Langmuir-Schaefer films deposited on indium-tin oxide substrates were observed to grow linearly with the number of layers, according to UV-visible absorption spectroscopy. Atomic force microscopy and Brewster angle microscopy were carried out for morphological characterization. From electrical transport measurements, the DC electrical conductivity of Langmuir-Schaefer films of P3AT was higher than the corresponding spin-coated films, which can be related to the dissimilar roughness and molecular-level organization provided by the Langmuir-Schaefer technique.

Molecular-Level Modifications Induced by Photo-Oxidation of Lipid Monolayers Interacting with Erythrosin.

Incorporation into cell membranes is key for the action of photosensitizers in photomedicine treatments, with hydroperoxidation as the prominent pathway of lipid oxidation. In this paper, we use Langmuir monolayers of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) as cell membrane models to investigate adsorption of the photosensitizer erythrosin and its effect on photoinduced lipid oxidation. From surface pressure isotherms and polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS) data, erythrosin was found to adsorb mainly via electrostatic interaction with the choline in the head groups of both DOPC and DPPC. It caused larger monolayer expansion in DOPC, with possible penetration into the hydrophobic unsaturated chains, while penetration into the DPPC saturated chains was insignificant. Easier penetration is due to the less packed DOPC monolayer, in comparison to the more compact DPPC according to the monolayer compressibility data. Most importantly, light irradiation at 530 nm made the erythrosin-containing DOPC monolayer become less unstable, with a relative surface area increase of ca. 19%, in agreement with previous findings for bioadhesive giant vesicles. The relative area increase is consistent with hydroperoxidation, supporting the erythrosin penetration into the lipid chains, which favors singlet oxygen generation close to double bonds, an important requirement for photodynamic efficiency.

Co-Deposition of Gold Nanoparticles and Metalloporphyrin Using the Langmuir-Blodgett (LB) Technique for Surface-Enhanced Raman Scattering (SERS).

The synergistic effect produced by metallic nanoparticles when incorporated into different systems empowers a research field that is growing rapidly. In addition, organometallic materials are at the center of intensive research with diverse applications such as light-emitting devices, transistors, solar cells, and sensors. The Langmuir-Blodgett (LB) technique has proven to be suitable to address challenges inherent to organic devices, since the film properties can be tuned at the molecular level. Here we report a strategy to incorporate gold nanoparticles (AuNPs) into the LB film by co-deposition in order to achieve surface-enhanced Raman scattering (SERS) of the zinc(II)-protoporphyrin (IX) dimethyl ester (ZnPPIX-DME). Prior to the LB co-deposition, the properties of the Langmuir monolayer of ZnPPIX-DME at the air-water interface, containing AuNPs in the subphase, are studied through the surface-pressure versus mean molecular area (π-A) isotherms. The ZnPPIX-DME+AuNPs π-A isotherm presented a significant shift to higher molecular area, suggesting an interaction between both ZnPPIX-DME molecules and AuNPs. Those interactions are a key factor allowing the co-deposition of both AuNPs and ZnPPIX-DME molecules onto a solid substrate, thus forming the LB film. SERS of ZnPPIX-DME was successfully attained, ensuring the spatial distribution of the AuNPs. Higher enhancement factors were found at AuNP aggregates, as a result of the intense local electromagnetic field found in the metal nanoparticle aggregates. The main vibrational bands observed in the SERS spectra suggest a physical adsorption of the ZnPPIX-DME onto the surface of AuNPs. The latter is not only in agreement with the interactions pointed out by the π-A isotherms but also suggests that this interaction is kept upon LB film co-deposition.