Surface plasmon enhanced linear and nonlinear optical properties of lycopene bioconjugated silver nanoparticles

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The ablation product was characterised by UV-Vis optical absorption, Raman spectroscopy and transmission electron microscopy (TEM). The experimental results were confirmed by the computational studies. Furthermore, to assess the influence of the surface plasmon on nonlinear optical (NLO) responses, in this work, we investigated the NLO properties of lycopene@silver systems using the density functional theory (DFT) approach at the B3LYP/6-311G/LANL2DZ level. In addition to molecular descriptors, the static and dynamic (at the working wavelength of the device, 1064 nm and 532 nm) polarizability (𝛼), first hyperpolarizability (β), and second hyperpolarizability (𝛾) were calculated. Compared to the lycopene molecule, results of the lycopene@Ag 18 system show increased values of +2.88 D, 115.86 x 10 -24 esu, 198.94 x 10 -30 esu, and 33.73 x 10 -34 esu, for 𝜇, 𝛼 0 , β 0 , and 𝛾 0 , respectively. We found that lycopene@Ag systems have enhanced NLO properties, allowing us to hypothesise that the lycopene@AgNPs with the increased size of the AgNPs might be suitable as third-order NLO materials with increased stability, high flexibility in molecular engineering, and flexible photonic devices. Bioconjugated lycopene with AgNPs enhances local field effects, boosting both linear and NLO attributes. Physical sciences/Engineering Physical sciences/Materials science Physical sciences/Mathematics and computing Physical sciences/Nanoscience and technology Physical sciences/Optics and photonics Physical sciences/Physics Lycopene Silver nanoparticles In-situ bioconjugation Nonlinear optical properties Density functional theory Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Introduction Research on innovative nanomaterials for possible applications in nonlinear optics is advancing markedly, propelled by their distinctive optical characteristics and the increasing need for sophisticated photonic devices. Carbon-based materials, such as organic dyes and graphene derivatives, have been extensively studied for their exceptional optical nonlinearities, attributable to their physicochemical, electronic, mechanical, and biomedical properties 1–5 . One of the most-interesting carbon-based materials used for nonlinear optical applications is lycopene. This naturally occurring carotenoid exhibits significant potential in photonic applications and photodynamic therapy due to its strong absorption in the visible region and its large third-order nonlinear susceptibility 6 . Lycopene is a 1D π-electrons conjugated carbon chain long molecule. Lycopene from tomato is a terpene consisting of 8 isoprene molecules with a chemical formulation of C40H56, constructed with two types of bonds: 11 alternative single-double carbon-carbon bonds along its backbone, two un-conjugated double bonds and no end groups . The molecule is structurally versatile: The electronic and NLO properties are tailored to the following factors: a huge quantity of π conjugated charge transfer and lengthening of the conjugation, a key component in the delocalisation of π-electrons-electrons during light excitation 7 .In contrast to these excellent properties, the lycopene produced by different approaches 8–11 has always been unstable and sensitive to photodegradation. Chemical and thermal stabilisation may be achieved by the conjugation with metal nanoparticles. Silver-based materials are widely used in the nonlinear optics field due to their excellent surface plasmon resonance 12–14 .In particular, silver nanoparticles (AgNPs) are one of the commonly used for surface plasmon sensors because of their high sensitivity to refractive index change, convenient synthesis, and high controllable degree of shape and size 15–19 .The efficient employment of Ag NPs, but also of other Ag materials, such as silver sulfide nanoparticles (AgS2 NPs), in nonlinear optics and sensing is related not only to their well-known surface plasmon resonance, but also to their saturable absorption for Q-Switching and refractive index sensor 20,21 . At the same time, natural phytocompounds, extracted from plants, fruit, leaves, and seeds are promising materials for linear and nonlinear optical applications such as optical limiting, optical sensing and photodynamic therapy 22–25 .Silver nanoparticles bioconjugated organic materials, including carbon nanotubes 26,27 ,graphene 28 ,dye 29,29 , and polymer 30–32 ,have shown an additional enhancement of the linear and nonlinear optical properties. Therefore, the natural lycopene bioconjugated AgNPs could show the same properties since they form a shell around NPs. Among the approaches developed to conjugate organic molecules or dye to metal nanoparticles, the pulsed laser ablation (PLAL) technique has gained great interest 33,34 ,since it provides high stability, high purity and high dispersibility. It allows the synthesis in a clean and green approach. There are several reports related to the ex-situ conjugation of organic molecules, dye and protein with laser-generated nanoparticles 35–37 .At the same time, only a few research groups have studied the laser-based in-situ conjugation method. For example, Binaymotlagh et al. 38 have studied the in-situ conjugation of the Au NPs-bovine serum albumin (AuNPs-BSA). Their results revealed that the in-situ laser ablation method has higher conjugation efficiency than the ex-situ conjugation. This study used the in-situ approach to construct the hybrid Lycopene@AgNPs by ablating a high-purity silver target into a pre-prepared lycopene solution (see the experimental section for further details). Furthermore, UV-Vis spectroscopy and surface-enhanced Raman spectroscopy have been employed to examine the influence of AgNPs on the linear optical characteristics and stability of the lycopene@AgNPs systems. The experimental results were intriguing, as the lycopene@AgNPs systems markedly enhanced the linear optical attributes in comparison to lycopene alone. We aim to model the interaction between lycopene molecules and ultrasmall silver nanoparticles and to evaluate their nonlinear optical properties. For the first time, we introduce three nanoclusters (Ag n NCs, n = 4, 8, 18) to examine their interaction with lycopene using DFT calculations and to find the optimal nanoparticle size for this interaction. Thus, we found that lycopene@AgNPs may be interesting candidates in photonics and photodynamic therapy due to their improved nonlinear optical properties. Materials and methods Samples synthesis . Lycopene powder (≥98% (HPLC), from tomato) was purchased from Sigma-Aldrich. The purity of the product was comparable to the previous studies 6 . The solution of lycopene was prepared by dissolving 0.05 mg of lycopene in 50 ml carbon disulfide (purchased from E-Merk, 99,9% purity). The obtained solution was stored at -20 ℃ to reduce the molecule aggregation and evaporation due to the solvent and adopted as the medium to ablate the silver target (99.99% purity). The in-situ bioconjugation developed by , Binaymotlagh et al. 38 was carried out by pulsed laser ablation of a silver target in the lycopene solution by using a Q-Switched Nd:YAG laser with a wavelength of 1064 nm (emitting 8 ns long pulses, and a repetition rate of 10 Hz), and ablation time of 20 min; see Figure 1 . Characterisation tools . A solidspec-3700 DUV230, A11094500005 unit within the spectral range of 250-800 nm was used to carry out the UV-Vis absorbance spectra of lycopene and lycopene@AgNPs, while a portable Raman Spectrometer (EZRaman- N Portable analyser system, Enwave Optronics, Inc.) equipped with a laser green excitation (785 nm laser line) was adopted to perform Raman measurements at room temperature. The UV-Vis Spectrophotometer and the Raman Spectrometer used in this project are both located at the Physics Department of the University of Nairobi. The TEM image was obtained using a FEI T20 with a 200 kV LaB6 filament based at the Electron Microscope Unit, at the University of Cape Town. The size distribution of the particles was determined from the TEM images using the ImageJ program. Computational methods . Since we expect a different size of AgNPs in the performed experiments, theses nanoparticles interact differently with lycopene molecule. For the first time, we have reported the interaction of neutral Ag n NCs (n=4,8,18) with lycopene molecules. DFT calculations were performed to investigate the optical properties of lycopene@Ag 4 , lycopene@Ag 8 , lycopene@Ag 18 , and lycopene. The Ag nanoclusters were constructed using the method proposed by Manna et al. 39 . The molecular structure of all analysed complexes was constructed using GaussView 6.0. All the calculations were performed with the Gaussian 09 program 40,41 by using the B3LYP functional, the 6-311G 42 basis set for carbon and hydrogen atoms, and the Lanl2DZ effective core potential with its accompanying basis set employed for Ag atoms 43 . The UV-Vis spectra were computed using the TD-B3LYP approach and the electronic transitions at the optimised ground-state geometry were calculated. Finally, the ground state dipole moment (𝜇), linear polarizability (𝛼) first hyperpolarizability (β), and second hyperpolarizability (𝛾) were investigated at B3LYP-6311G/Lanl2DZ to further probe the NLO properties of lycopene@Ag n systems. The values of the ground state dipole moment, mean polarizability, and the anisotropy of the polarizability and hyperpolarizability was calculated using the following equations. Results and discussion Linear optical investigations .In order to characterise and monitor the structural changes of as-prepared samples, UV-Vis absorption spectroscopy and Raman spectroscopy were carried out. The Raman spectra of lycopene and lycopene@AgNPs composites are shown in Figure 2 a . The samples were excited looking at the classical fingerprints of lycopene electronic transitions within the spectral range of 250-800 nm. Lycopene shows 3 principal absorbance peaks centered at 476, 504, and 540 nm respectively, and a low-intensity peak in the UV region at 348 nm, which originate from the various π-π* and σ-σ* transitions 6 . As suggested by Hager, the absorbance peak at 348 nm is due to an aggregation of the pigment molecules and the solvent molecules 44 . As seen from Figure 2 a , the lycopene@AgNPs showed an increase in the intensity of the absorption bands. An enhancement of the lycopene absorbance in the presence of AgNPs is clearly noticeable. Dividing the absorbance intensity of lycopene in the presence of AgNPs from that in the absence of AgNPs yields an enhancement factor of 1.97. It is clear that AgNPs seem to provide remarkable protection to lycopene against photodegradation. Photodegradation is characterised by the decrease in the intensity of the absorption bands on the exposure of lycopene to red light 45 . Thus, the results demonstrated that lycopene was successfully conjugated with AgNPs, and the absorbance enhancement observed in this current work could be understood as a result of the modification of the local electromagnetic field in the vicinity of lycopene caused by the localised surface plasmon resonance at the surface of AgNPs. The Raman spectra of lycopene and lycopene@AgNPs are shown in Figure 2 b . Lycopene displays two intense peaks at 1152 cm -1 and 1514 cm -1 , related to C-C single and double bond vibrations of the conjugated backbone of the lycopene molecule 6 . However, the observed weak peaks at 830 cm -1 ,1002 cm -1 , 1282 cm -1 and 1454 cm -1 could be attributed to the CH deformation. After conjugating with AgNPs, for various signature Raman shift peaks between 830 cm -1 to 1514 cm -1 , the intensities of the Raman signals of the product simultaneously enhanced due to the plasmon effect of AgNPs 46 . The lycopene bioconjugated AgNPs showed 2.3 times more enhancement compared to lycopene alone. The electromagnetic field is more confined in the narrower region of the lycopene@AgNPs, which leads to a more effective enhancement at the junction between the AgNPs 47 . The TEM image and the size distribution histogram of AgNPs generated by the laser ablation in the lycopene solution are shown in Figure 3 a . From the TEM image, the AgNPs were found to have a spherical morphology with a broad size distribution. According to the size distribution histogram, the AgNPs yield an average size of 16.53 nm; see Figure 3 b . The TD-DFT simulations calculated the maximum absorption wavelength of pure lycopene and lycopene@Ag n systems at B3LYP/6-311G/Lanl2DZ in gas phases to rationalise the nature of transitions and the interaction between the two species. The results showed a very favourable interaction between lycopene and AgNCs: the calculated interaction energies increased with the size of the silver nanocluster; however, the differences became smaller going from lycopene@Ag 4 to lycopene@Ag 18 . From Table 1 , it is observed that the experimental λ max values for all investigated compounds are quite close to the calculated λ max values, which suggests a considerable stability of the conjugates. The maximum absorption wavelength was found at 583.98 nm for lycopene@Ag 8 ; a moderate redshift was observed with the maximum absorption of 583.98 nm for lycopene@Ag 18 ; see Figure 4 . Figure 5 reports the frontier molecular orbital (FMO) energy levels diagram. FMO is critical in explaining doped complexes’ charge flow and electron distribution strategies 48 . As can be seen from Table 2 , the HOMO-LUMO gap ranges from 2.10 eV to 1.48 eV. From Figure 4, the HOMO level of lycopene@Ag 4 was localised both to the AgNC and lycopene’s carbon-carbon unconjugated double bond, whereas the LUMO level was localised only to the AgNC. This tunes the energy gap compared to lycopene. The HOMO and LUMO levels of lycopene@Ag 8 were localised to the lycopene and resulted in the energy gap equal to that of lycopene. The HOMO level of lycopene@Ag 18 was localized to the lycopene. In contrast, the LUMO level showed the delocalisation of the electron distribution to the AgNC, resulting in the decrease of the energy gap. These findings suggest that doping lycopene with AgNCs leads to a decrease in the energy gap. Among the studied systems, lycopene@Ag 4 and lycopene@Ag 18 exhibit the lowest E g and are considered suitable candidates for OLEDs. Therefore, these conjugated complexes are promising materials for NLO applications. Nonlinear optical investigations .The dipole moment is an important parameter to describe the charge distribution of the complexes and to understand the polarisation of the molecule. It also plays a crucial role in structural chemistry and crystallinity thanks to its sensitivity to small changes in the structure of the molecule. Doping impacts the optoelectronic properties of doped complexes, including dipole moment and transition energy 48 . Table 3 presents the calculated dipole moments of lycopene, lycopene@Ag 4 , lycopene@Ag 8 , and lycopene@Ag 18 . Lycopene has a 0.61 D dipole moment, according to a report 6 . When doping with AgNCs at a specific position of the molecule (more detail in MEP analysis, section 3.4), they produced greater values in π-conjugation. As expected, lycopene@Ag n systems present a larger dipole moment than pure lycopene, although lycopene@Ag 8 shows the highest dipole moment due to the T d symmetry structure of Ag 8 NC. However, lycopene@Ag 4 and lycopene@Ag 18 present a closed dipole moment due to the D 2h and C s symmetry structure of the Ag 4 NC and Ag 18 NC, respectively. The dipole moment increasing order for all computed compounds according to Lycopene < lycopene@Ag 4 < lycopene@Ag 18 <lycopene@Ag 8 . In order to understand the NLO response of the lycopene molecule bioconjugated with AgNPs, we calculated the polarizability and hyperpolarizability of pure lycopene and lycopene@Ag n NCs (n=4, 8, 18). The calculated polarizabilities and hyperpolarizabilities for all computed compounds at the B3LYP functional are presented in Table 3 and Figure 6 . The choice of this functional is based on the work of Patil and Sekar, who proved that B3LYP predicted higher values of 𝛼 0 , β 0 , and 𝛾 than CAM-B3LYP in the gas phase and in comparison to other commonly used functionals 49 . The polarizability (𝛼 0 ) value for pure lycopene is 171.08 10 -24 esu. Conjugating with AgNCs significantly enhances polarizability, in all lycopene@Ag n conjugates. The polarizability (𝛼 0 ) values for lycopene@Ag 4 NC, lycopene@Ag 8 NC and lycopene@Ag 18 NC are 206.54 10 -24 esu, 230.21 10 -24 esu, and 286.94 10 -24 esu, respectively. Compared to lycopene as a reference the lycopene@Ag 18 indicates the highest polarizability (𝛼 0 ). The first-order hyperpolarizability (β 0 ) for pure lycopene is 10.73 10 -30 esu. However, a significant change in β 0 is observed in the lycopene@Ag n conjugates. Lycopene@Ag 18 NC indicates the highest value (209.67 10 -30 esu) than all other complexes. The study found that as the size of the nanoclusters increased, the β 0 also increased linearly in the order of Ag 4 NC < Ag 8 NC < Ag 18 NC. The overall increasing order for β 0 value is Lycopene < lycopene@Ag 4 NC < lycopene@Ag 8 NC < lycopene@Ag 18 NC. In second-order hyperpolarizability (𝛾), lycopene@Ag 18 indicates the highest values (189.16 10 -34 esu) to other lycopene@Ag n conjugates. Therefore, the large values of 𝛾 permit us to conclude that these complexes have excellent linear and nonlinear optical properties and hence can be used in third-order nonlinear optical materials, which may have optoelectronic, photonic, and photodynamic therapy applications. The second-order nonlinearity can be obtained by combining two properties: the product of dipole moment (𝜇) and first-order hyperpolarizability (β 0 ) 50 . From Table 3 one can observe that compared to pure lycopene, larger values of 𝜇 β 0 are obtained for lycopene@Ag 4 , lycopene@Ag 8 , and lycopene@Ag 18 . Frequency-dependent calculations were performed to evaluate the nonlinear response of the material at the operating wavelength during laser excitation for a particular device application 51 . Second harmonic generation (SHG), electro-optical Pockel’s effect (EOPE), electric field-induced second harmonic generation (ESHG) and the dc-Kerr effect were studied at 1064 nm, 532 nm, and the wavelength of the Nd:YAG laser 52 . Hence, the hyperpolarizability coefficients for SHG β(-2𝜔; 𝜔, 𝜔), EOPE β(-𝜔; 𝜔, 0), ESHG 𝛾(-2𝜔; 𝜔, 𝜔, 0), and dc-Kerr effect 𝛾(-𝜔; 𝜔, 0, 0) were calculated at 1064nm and 532 nm wavelength in B3LYP functional. The second- and third-order NLO coefficients for lycopene and lycopene@Ag n NCs are listed in Table 4 and Table 5 , respectively. The SHG and EOPE values at 532 nm were higher than the values at 1064 nm for all the investigated compounds. Among these compounds, lycopene@Ag 18 demonstrated the highest SHG and EOPE; see Table 4 . From Table 5 , lycopene@Ag 18 showed larger dc-Kerr effect and ESHG values, and their values at 532 nm were higher than those at 1064 nm. Therefore, for both second- and third-order NLO coefficients, the values at 532 nm were higher than the values at 1064 nm for the studied compounds. From these results, we conclude that the dc-Kerr effect is the significant third-order NLO effect in lycopene and lycopene@Ag n at 532 nm. This model can be used to predict the NLO effect of the material and the frequency of the laser at which the NLO coefficients would be wider. Quantitative molecular electrostatic potential (MEP) and difference density analysis . The MEP descriptor is usually used to analyse charge transfer efficiency, soft-soft and hard-hard interaction, and the distribution of charge density among the complexes 49 . Figure 7 a displays the MEP maps of all the analysed components. Lycopene’s MEP is dominated by red along the linear carbon chain of the molecule, which represents the negative value of the electron density, thus making it more electrophilic. The electron density distribution in lycopene also revealed the red-hued zone at the two opposite ends of the molecule located in the two unconjugated C-C double bonds. These regions are very rich in electrons and can donate electron density to the orbitals of Ag atoms in the cluster. Based on our findings, the Ag clusters were bonded with lycopene in that specific region. Therefore, the region containing the AgNCs dopant and the backbone chain of lycopene is blue (positive value) and acts as nucleophiles. For the difference density, the blue region represents the positive value of the difference density, i.e., where the excited state density is larger than the ground state density. The red region indicates the reverse. Therefore, for lycopene, electron density moves from the region of the C-C double bonds to the region of the C-C single bonds as it transitions from the ground state to the first excited state; see Figure 7 b . Conclusion In the present work, we have demonstrated the enhancement of linear and NLO properties of lycopene bioconjugated silver nanoparticles. The absorbance intensity and the Raman intensity of the lycopene@Ag system substantially increased due to the improved excitation rate of silver nanoparticles. The TEM image showed that the pulsed laser ablation of a silver target in lycopene solution generated stable AgNPs with an average size of 16.53 nm. In the computational model, the lycopene@AgNCs interaction was studied. As silver models, the Ag 4 , Ag 8 and Ag 18 were proposed to investigate their linear and NLO properties. After performing the MEP of lycopene, the AgNCs were placed at the most electrophilic region of the molecule, which acts as the most stable binding site. The vertical excitation values were found to be closer to the experimental absorption maxima. The calculated 𝛼 0 , β 0 , and 𝛾 0 values of lycopene@AgNCs increased compared to lycopene and improved with the increasing size of the AgNCs. From the Frequency-dependent NLO properties at 1064 nm and 532 nm wavelength, it was observed that various second- and third-order NLO parameters, such as SHG β(-2𝜔; 𝜔, 𝜔), EOPE β(-𝜔; 𝜔, 0), and ESHG 𝛾(-2𝜔; 𝜔, 𝜔, 0), and dc-Kerr effect 𝛾(-𝜔; 𝜔, 0, 0), respectively, of lycopene@AgNCs also improved with the size of the AgNCs. Therefore, the dc-Kerr effect is the major third-order NLO effect in lycopene and lycopene@Ag n at 532 nm. For the understanding of the third-order NLO effect related to the third-order NLO susceptibility, future deeper investigations are needed toward the Z-scan analysis technique. Declarations Acknowledgements We are grateful to the various supporting institutions, including the University of South Africa, iThemba LABS (ITLABS), the National Research Foundation of South Africa (NRF), the African Laser Centre (ALC), the international Organization of Women in Science (OWSD), the Abdus Salam International Centre for Theoretical Physics (The Abdus Salam-ICTP), the Royal Society-London and naturally the United Nations Education, Sciences & Culture Organization (UNESCO) as well as the French Foreign Ministry and the ADESFA program. Likewise, the Centre for High Performance Computation (CHPC) is acknowledged. The first author gratefully acknowledges the support from Triangle Science, Education & Economic Development, LLC (TriSEED Consultant, LLC). Author contributions E. L. T. N.: Conceptualisation, methodology, sample preparation, Modelling & computational studies, Data analysis, Writing original draft. N. M. 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Tables Tables 1 to 5 are available in the Supplementary Files section Additional Declarations No competing interests reported. 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Africa","correspondingAuthor":false,"prefix":"","firstName":"Nancy","middleName":"Mwikali","lastName":"Mwenze","suffix":""},{"id":451687915,"identity":"49b27357-e9be-44d9-a6e8-372723db5634","order_by":2,"name":"Mahouton Norbert Hounkonnou","email":"","orcid":"","institution":"Université d'Abomey-Calavi","correspondingAuthor":false,"prefix":"","firstName":"Mahouton","middleName":"Norbert","lastName":"Hounkonnou","suffix":""},{"id":451687917,"identity":"307be1cd-d168-4e6e-9995-922b1bdc3ba5","order_by":3,"name":"Malik Maaza","email":"","orcid":"","institution":"University of South Africa","correspondingAuthor":false,"prefix":"","firstName":"Malik","middleName":"","lastName":"Maaza","suffix":""}],"badges":[],"createdAt":"2025-04-21 19:23:08","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6498356/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6498356/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41598-025-13103-2","type":"published","date":"2025-07-25T15:58:22+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":82166515,"identity":"f8c6a3e4-d909-47cc-b06d-3d6713c2253d","added_by":"auto","created_at":"2025-05-07 09:13:35","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":140234,"visible":true,"origin":"","legend":"\u003cp\u003eA representation of the in-situ bioconjugation method for the synthesis of the hybrid lycopene@AgNPs by PLAL.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-6498356/v1/3b87cb3df3096c84d86d7bcf.png"},{"id":82167328,"identity":"7195ff30-1429-4c39-bc5e-59f74080e914","added_by":"auto","created_at":"2025-05-07 09:21:35","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":311859,"visible":true,"origin":"","legend":"\u003cp\u003e(a) UV-Vis optical absorption and (b) Raman spectra of lycopene and lycopene@AgNPs.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-6498356/v1/dee360852a02e65291325cdb.png"},{"id":82166520,"identity":"9770683c-03a3-49bd-8608-4cd3b69efb17","added_by":"auto","created_at":"2025-05-07 09:13:35","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":538806,"visible":true,"origin":"","legend":"\u003cp\u003e(a) TEM image and (b) size distribution histogram of the AgNPs prepared by the in-situ method in lycopene solution (the lycopene@AgNPs bioconjugated system).\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-6498356/v1/57da58444d38edbc81e05b20.png"},{"id":82166519,"identity":"bceedebf-3fc4-478d-b9d5-a949a96600bd","added_by":"auto","created_at":"2025-05-07 09:13:35","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":157680,"visible":true,"origin":"","legend":"\u003cp\u003eAbsorption spectra of lycopene@Agn, n=4,8,18 at B3LYP/6-311G/LANL2DZ level of theory.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-6498356/v1/735917efe4ad76cc398afc71.png"},{"id":82166529,"identity":"e3e1ce26-b2f8-46b4-8cd3-913e71e69b8e","added_by":"auto","created_at":"2025-05-07 09:13:35","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":198898,"visible":true,"origin":"","legend":"\u003cp\u003eFrontier molecular orbital (FMO) representation of lycopene and lycopene@Agn, n=4,8,18 at B3LYP/6-311G/LANL2DZ level of theory.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-6498356/v1/d3f4a729f204db3f0149a5c8.png"},{"id":82166526,"identity":"2e4d1df4-34ee-452c-ae71-2f2e6c75614d","added_by":"auto","created_at":"2025-05-07 09:13:35","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":163515,"visible":true,"origin":"","legend":"\u003cp\u003eRepresented polarizabilities (esu) of lycopene and lycopene@Agn (n=4,8,18) at B3LYP/6-311G/LANl2DZ level.\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-6498356/v1/d28ea290a8a198a4b7a0e61f.png"},{"id":82166523,"identity":"0abcf79f-5a03-49ce-bbe7-a371a011b40d","added_by":"auto","created_at":"2025-05-07 09:13:35","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":416152,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Electrostatic potential of lycopene and lycopene@AgnNCs at B3LYP/6-311G/LANL2DZ and (b) difference density of lycopene at TD-B3LYP/6-311G/LANL2DZ.\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-6498356/v1/0c654145c4b8ee45bc0e2c14.png"},{"id":87757666,"identity":"0690db4d-60a9-4084-afa5-50adf197f5e8","added_by":"auto","created_at":"2025-07-28 16:11:17","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2650324,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6498356/v1/552e464e-4a30-40e5-b353-6c5dd715f24d.pdf"},{"id":82166516,"identity":"b21687de-0189-4d7b-99dd-1fdbede68456","added_by":"auto","created_at":"2025-05-07 09:13:35","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":50661,"visible":true,"origin":"","legend":"","description":"","filename":"Tables.docx","url":"https://assets-eu.researchsquare.com/files/rs-6498356/v1/5350f760ed6c2bba372f6e35.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Surface plasmon enhanced linear and nonlinear optical properties of lycopene bioconjugated silver nanoparticles","fulltext":[{"header":"Introduction","content":"\u003cp\u003eResearch on innovative nanomaterials for possible applications in nonlinear optics is advancing markedly, propelled by their distinctive optical characteristics and the increasing need for sophisticated photonic devices. Carbon-based materials, such as organic dyes and graphene derivatives, have been extensively studied for their exceptional optical nonlinearities, attributable to their physicochemical, electronic, mechanical, and biomedical properties\u003csup\u003e1–5\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eOne of the most-interesting carbon-based materials used for nonlinear optical applications is lycopene. This naturally occurring carotenoid exhibits significant potential in photonic applications and photodynamic therapy due to its strong absorption in the visible region and its large third-order nonlinear susceptibility\u003csup\u003e6\u003c/sup\u003e\u003cstrong\u003e.\u0026nbsp;\u003c/strong\u003eLycopene is a 1D π-electrons conjugated carbon chain long molecule. Lycopene from tomato is a terpene consisting of 8 isoprene molecules with a chemical formulation of C40H56, constructed with two types of bonds: 11 alternative single-double carbon-carbon bonds along its backbone, two un-conjugated double bonds and no end groups\u003cstrong\u003e.\u0026nbsp;\u003c/strong\u003eThe molecule is structurally versatile: \u0026nbsp;The electronic and NLO properties are tailored to the following factors: a huge quantity of π conjugated charge transfer and lengthening of the conjugation, a key component in the delocalisation of π-electrons-electrons during light excitation\u003csup\u003e7\u003c/sup\u003e.In contrast to these excellent properties, the lycopene produced by different approaches\u003csup\u003e8–11\u003c/sup\u003ehas \u0026nbsp;always been unstable and sensitive to photodegradation. Chemical and thermal stabilisation may be achieved by the conjugation with metal nanoparticles.\u003c/p\u003e\n\u003cp\u003eSilver-based materials are widely used in the nonlinear optics field due to their excellent surface plasmon resonance\u003csup\u003e12–14\u003c/sup\u003e.In particular, silver nanoparticles (AgNPs) are one of the commonly used for surface plasmon sensors because of their high sensitivity to refractive index change, convenient synthesis, and high controllable degree of shape and size\u003csup\u003e15–19\u003c/sup\u003e.The efficient employment of Ag NPs, but also of other Ag materials, such as silver sulfide nanoparticles (AgS2 NPs), in nonlinear optics and sensing is related not only to their well-known surface plasmon resonance, but also to their saturable absorption for Q-Switching and refractive index sensor\u003csup\u003e20,21\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eAt the same time, natural phytocompounds, extracted from plants, fruit, leaves, and seeds are promising materials for linear and nonlinear optical applications such as optical limiting, optical sensing and photodynamic therapy\u003csup\u003e22–25\u003c/sup\u003e.Silver nanoparticles bioconjugated organic materials, including carbon nanotubes\u003csup\u003e26,27\u003c/sup\u003e,graphene \u003csup\u003e28\u003c/sup\u003e,dye\u003csup\u003e29,29\u003c/sup\u003e, and polymer\u003csup\u003e30–32\u003c/sup\u003e,have shown an additional enhancement of the linear and nonlinear optical properties. Therefore, the natural lycopene bioconjugated AgNPs could show the same properties since they form a shell around NPs. Among the approaches developed to conjugate organic molecules or dye to metal nanoparticles, the pulsed laser ablation (PLAL) technique has gained great interest\u003csup\u003e33,34\u003c/sup\u003e,since it provides high stability, high purity and high dispersibility. It allows the synthesis in a clean and green approach. There are several reports related to the ex-situ conjugation of organic molecules, dye and protein with laser-generated nanoparticles\u003csup\u003e35–37\u003c/sup\u003e.At the same time, only a few research groups have studied the laser-based in-situ conjugation method. For example, Binaymotlagh et al. \u003csup\u003e38\u003c/sup\u003e have studied the in-situ conjugation of the Au NPs-bovine serum albumin (AuNPs-BSA). Their results revealed that the in-situ laser ablation method has higher conjugation efficiency than the ex-situ conjugation.\u003c/p\u003e\n\u003cp\u003eThis study used the in-situ approach to construct the hybrid Lycopene@AgNPs by ablating a high-purity silver target into a pre-prepared lycopene solution (see the experimental section for further details). Furthermore, UV-Vis spectroscopy and surface-enhanced Raman spectroscopy have been employed to examine the influence of AgNPs on the linear optical\u0026nbsp;characteristics\u0026nbsp;and\u0026nbsp;stability\u0026nbsp;of\u0026nbsp;the\u0026nbsp;lycopene@AgNPs\u0026nbsp;systems. The experimental results were intriguing, as the lycopene@AgNPs systems markedly enhanced the linear optical attributes in comparison to lycopene alone.\u003c/p\u003e\n\u003cp\u003eWe aim to model the interaction between lycopene molecules and ultrasmall silver nanoparticles and to evaluate their nonlinear optical properties. For the first time, we introduce three nanoclusters (Ag\u003csub\u003en\u003c/sub\u003eNCs, n = 4, 8, 18) to examine their interaction with lycopene using DFT calculations and to find the optimal nanoparticle size for this interaction. Thus, we found that lycopene@AgNPs may be interesting candidates in photonics and photodynamic therapy due to their improved nonlinear optical properties.\u003c/p\u003e"},{"header":"Materials and methods","content":"\u003cp\u003e\u003cstrong\u003eSamples synthesis\u003c/strong\u003e. Lycopene powder (\u0026ge;98% (HPLC), from tomato) was purchased from Sigma-Aldrich. The purity of the product was comparable to the previous studies \u003csup\u003e6\u003c/sup\u003e. The solution of lycopene was prepared by dissolving 0.05 mg of lycopene in 50 ml carbon disulfide (purchased from E-Merk, 99,9% purity). The obtained solution was stored at -20 ℃ to reduce the molecule aggregation and evaporation due to the solvent and adopted as the medium to ablate the silver target (99.99% purity). The in-situ bioconjugation developed by , Binaymotlagh et al. \u003csup\u003e38\u003c/sup\u003e was carried out by pulsed laser ablation of a silver target in the lycopene solution by using a Q-Switched Nd:YAG laser with a wavelength of 1064 nm (emitting 8 ns long pulses, and a repetition rate of 10 Hz), and ablation time of 20 min; see \u003cstrong\u003eFigure 1\u003c/strong\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCharacterisation tools\u003c/strong\u003e. A solidspec-3700 DUV230, A11094500005 unit within the spectral range of 250-800 nm was used to carry out the UV-Vis absorbance spectra of lycopene and lycopene@AgNPs, while a portable Raman Spectrometer (EZRaman- N Portable analyser system, Enwave Optronics, Inc.) equipped with a laser green excitation (785 nm laser line) was adopted to perform Raman measurements at room temperature. The UV-Vis Spectrophotometer and the Raman Spectrometer used in this project are both located at the Physics Department of the University of Nairobi. The TEM image was obtained using a FEI T20 with a 200 kV LaB6 filament based at the Electron Microscope Unit, at the University of Cape Town. The size distribution of the particles was determined from the TEM images using the ImageJ program.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eComputational methods\u003c/strong\u003e. Since we expect a different size of AgNPs in the performed experiments, theses nanoparticles interact differently with lycopene molecule. For the first time, we have reported the interaction of neutral Ag\u003csub\u003en\u003c/sub\u003eNCs (n=4,8,18) with lycopene molecules.\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eDFT calculations were performed to investigate the optical properties of lycopene@Ag\u003csub\u003e4\u003c/sub\u003e, lycopene@Ag\u003csub\u003e8\u003c/sub\u003e, lycopene@Ag\u003csub\u003e18\u003c/sub\u003e, and lycopene. The Ag nanoclusters were constructed using the method proposed by Manna et al. \u003csup\u003e39\u003c/sup\u003e. The molecular structure of all analysed complexes was constructed using GaussView 6.0. All the calculations were performed with the Gaussian 09 program \u003csup\u003e40,41\u003c/sup\u003e by using the B3LYP functional, the 6-311G\u003csup\u003e42\u003c/sup\u003e basis set for carbon and hydrogen atoms, and the Lanl2DZ effective core potential with its accompanying basis set employed for Ag atoms \u003csup\u003e43\u003c/sup\u003e. The UV-Vis spectra were computed using the TD-B3LYP approach and the electronic transitions at the optimised ground-state geometry were calculated. Finally, the ground state dipole moment (𝜇), linear polarizability (𝛼) first hyperpolarizability (\u0026beta;), and second hyperpolarizability (𝛾) were investigated at B3LYP-6311G/Lanl2DZ to further probe the NLO properties of lycopene@Ag\u003csub\u003en\u003c/sub\u003e systems.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe values of the ground state dipole moment, mean polarizability, and the anisotropy of the polarizability and hyperpolarizability was calculated using the following equations.\u003c/p\u003e\n\u003cp\u003e\u003cimg 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\"\u003e\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cp\u003e\u003cstrong\u003eLinear optical investigations\u003c/strong\u003e.In order to characterise and monitor the structural changes of as-prepared samples, UV-Vis absorption spectroscopy and Raman spectroscopy were carried out. The Raman spectra of lycopene and lycopene@AgNPs composites are shown in\u0026nbsp;\u003cstrong\u003eFigure 2\u003c/strong\u003e\u003cstrong\u003ea\u003c/strong\u003e. The samples were excited looking at the classical fingerprints of lycopene electronic transitions within the spectral range of 250-800 nm. Lycopene shows 3 principal absorbance peaks centered at 476, 504, and 540 nm respectively, and a low-intensity peak in the UV region at 348 nm, which originate from the various π-π* and σ-σ* transitions \u003csup\u003e6\u003c/sup\u003e. As suggested by Hager, the absorbance peak at 348 nm is due to an aggregation of the pigment molecules and the solvent molecules \u003csup\u003e44\u003c/sup\u003e. As seen from\u0026nbsp;\u003cstrong\u003eFigure 2\u003c/strong\u003e\u003cstrong\u003ea\u003c/strong\u003e, the lycopene@AgNPs showed an increase in the intensity of the absorption bands. An enhancement of the lycopene absorbance in the presence of AgNPs is clearly noticeable. Dividing the absorbance intensity of lycopene in the presence of AgNPs from that in the absence of AgNPs yields an enhancement factor of 1.97. It is clear that AgNPs seem to provide remarkable protection to lycopene against photodegradation. Photodegradation is characterised by the decrease in the intensity of the absorption bands on the exposure of lycopene to red light\u0026nbsp;\u003csup\u003e45\u003c/sup\u003e. Thus, the results demonstrated that lycopene was successfully conjugated with AgNPs, and the absorbance enhancement observed in this current work could be understood as a result of the modification of the local electromagnetic field in the vicinity of lycopene caused by the localised surface plasmon resonance at the surface of AgNPs.\u003c/p\u003e\n\u003cp\u003eThe Raman spectra of lycopene and lycopene@AgNPs are shown in \u003cstrong\u003eFigure 2\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e. Lycopene displays two intense peaks at 1152 cm\u003csup\u003e-1\u003c/sup\u003e and 1514 cm\u003csup\u003e-1\u003c/sup\u003e, related to C-C single and double bond vibrations of the conjugated backbone of the lycopene molecule \u003csup\u003e6\u003c/sup\u003e. However, the observed weak peaks at 830 cm\u003csup\u003e-1\u003c/sup\u003e,1002 cm\u003csup\u003e-1\u003c/sup\u003e, 1282 cm\u003csup\u003e-1\u003c/sup\u003e and 1454 cm\u003csup\u003e-1\u003c/sup\u003e could be attributed to the CH deformation. After conjugating with AgNPs, for various signature Raman shift peaks between 830 cm\u003csup\u003e-1\u003c/sup\u003e to 1514 cm\u003csup\u003e-1\u003c/sup\u003e, the intensities of the Raman signals of the product simultaneously enhanced due to the plasmon effect of AgNPs \u003csup\u003e46\u003c/sup\u003e. The lycopene bioconjugated AgNPs showed 2.3 times more enhancement compared to lycopene alone. The electromagnetic field is more confined in the narrower region of the lycopene@AgNPs, which leads to a more effective enhancement at the junction between the AgNPs \u003csup\u003e47\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eThe TEM image and the size distribution histogram of AgNPs generated by the laser ablation in the lycopene solution are shown in\u0026nbsp;\u003cstrong\u003eFigure 3\u003c/strong\u003e\u003cstrong\u003ea\u003c/strong\u003e. From the TEM image, the AgNPs were found to have a spherical morphology with a broad size distribution. According to the size distribution histogram, the AgNPs yield an average size of 16.53 nm; see\u0026nbsp;\u003cstrong\u003eFigure 3\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e.\u003c/p\u003e\n\u003cp\u003eThe TD-DFT simulations calculated the maximum absorption wavelength of pure lycopene and lycopene@Ag\u003csub\u003en\u003c/sub\u003e systems at B3LYP/6-311G/Lanl2DZ in gas phases to rationalise the nature of transitions and the interaction between the two species. The results showed a very favourable interaction between lycopene and AgNCs: the calculated interaction energies increased with the size of the silver nanocluster; however, the differences became smaller going from lycopene@Ag\u003csub\u003e4\u003c/sub\u003e to lycopene@Ag\u003csub\u003e18\u003c/sub\u003e. From \u003cstrong\u003eTable 1\u003c/strong\u003e, it is observed that the experimental λ\u003csub\u003emax\u003c/sub\u003e values for all investigated compounds are quite close to the calculated λ\u003csub\u003emax\u003c/sub\u003e values, which suggests a considerable stability of the conjugates. The maximum absorption wavelength was found at 583.98 nm for lycopene@Ag\u003csub\u003e8\u003c/sub\u003e; a moderate redshift was observed with the maximum absorption of 583.98 nm for lycopene@Ag\u003csub\u003e18\u003c/sub\u003e; see \u003cstrong\u003eFigure 4\u003c/strong\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFigure 5\u003c/strong\u003e reports the frontier molecular orbital (FMO) energy levels diagram. FMO is critical in explaining doped complexes’ charge flow and electron distribution strategies \u003csup\u003e48\u003c/sup\u003e. As can be seen from\u003cstrong\u003eTable 2\u003c/strong\u003e, the HOMO-LUMO gap ranges from 2.10 eV to 1.48 eV. From Figure 4, the HOMO level of lycopene@Ag\u003csub\u003e4\u003c/sub\u003e was localised both to the AgNC and lycopene’s carbon-carbon unconjugated double bond, whereas the LUMO level was localised only to the AgNC. This tunes the energy gap compared to lycopene. The HOMO and LUMO levels of lycopene@Ag\u003csub\u003e8\u003c/sub\u003e were localised to the lycopene and resulted in the energy gap equal to that of lycopene. The HOMO level of lycopene@Ag\u003csub\u003e18\u003c/sub\u003e was localized to the lycopene. In contrast, the LUMO level showed the delocalisation of the electron distribution to the AgNC, resulting in the decrease of the energy gap. These findings suggest that doping lycopene with AgNCs leads to a decrease in the energy gap. Among the studied systems, lycopene@Ag\u003csub\u003e4\u003c/sub\u003e and lycopene@Ag\u003csub\u003e18\u003c/sub\u003e exhibit the lowest E\u003csub\u003eg\u003c/sub\u003e and are considered suitable candidates for OLEDs. Therefore, these conjugated complexes are promising materials for NLO applications.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eNonlinear optical investigations\u003c/strong\u003e.The dipole moment is an important parameter to describe the charge distribution of the complexes and to understand the polarisation of the molecule. It also plays a crucial role in structural chemistry and crystallinity thanks to its sensitivity to small changes in the structure of the molecule. Doping impacts the optoelectronic properties of doped complexes, including dipole moment and transition energy \u003csup\u003e48\u003c/sup\u003e.\u0026nbsp;\u003cstrong\u003eTable 3\u003c/strong\u003e presents the calculated dipole moments of lycopene, lycopene@Ag\u003csub\u003e4\u003c/sub\u003e, lycopene@Ag\u003csub\u003e8\u003c/sub\u003e, and lycopene@Ag\u003csub\u003e18\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003eLycopene has a 0.61 D dipole moment, according to a report \u003csup\u003e6\u003c/sup\u003e. When doping with AgNCs at a specific position of the molecule (more detail in MEP analysis, section 3.4), they produced greater values in π-conjugation. As expected, lycopene@Ag\u003csub\u003en\u003c/sub\u003e systems present a larger dipole moment than pure lycopene, although lycopene@Ag\u003csub\u003e8\u003c/sub\u003e shows the highest dipole moment due to the T\u003csub\u003ed\u003c/sub\u003e symmetry structure of Ag\u003csub\u003e8\u003c/sub\u003eNC. However, lycopene@Ag\u003csub\u003e4\u0026nbsp;\u003c/sub\u003eand lycopene@Ag\u003csub\u003e18\u003c/sub\u003e present a closed dipole moment due to the D\u003csub\u003e2h\u003c/sub\u003e and C\u003csub\u003es\u003c/sub\u003e symmetry structure of the Ag\u003csub\u003e4\u003c/sub\u003eNC and Ag\u003csub\u003e18\u003c/sub\u003eNC, respectively. The dipole moment increasing order for all computed compounds according to Lycopene \u0026lt; lycopene@Ag\u003csub\u003e4\u003c/sub\u003e \u0026lt; lycopene@Ag\u003csub\u003e18\u003c/sub\u003e \u0026lt;lycopene@Ag\u003csub\u003e8\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003eIn order to understand the NLO response of the lycopene molecule bioconjugated with AgNPs, we calculated the polarizability and hyperpolarizability of pure lycopene and lycopene@Ag\u003csub\u003en\u003c/sub\u003eNCs (n=4, 8, 18). The calculated polarizabilities and hyperpolarizabilities for all computed compounds at the B3LYP functional are presented in \u003cstrong\u003eTable 3\u003c/strong\u003e and \u003cstrong\u003eFigure 6\u003c/strong\u003e. The choice of this functional is based on the work of Patil and Sekar, who proved that B3LYP predicted higher values of\u0026nbsp;𝛼\u003csub\u003e0\u003c/sub\u003e, β\u003csub\u003e0\u003c/sub\u003e, and\u0026nbsp;𝛾\u0026nbsp;than CAM-B3LYP in the gas phase and in comparison to other commonly used functionals\u0026nbsp;\u003csup\u003e49\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eThe polarizability (𝛼\u003csub\u003e0\u003c/sub\u003e) value for pure lycopene is 171.08\u0026nbsp;\u003cimg width=\"11\" height=\"19\" src=\"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAABAAAAAcBAMAAACaHyIpAAAAAXNSR0IArs4c6QAAACpQTFRFAAAAAAAAAAA6OpC2OpDbZrbbZrb/kDo6kNv/tmYAtmY625A625Bm///b97lStQAAAAF0Uk5TAEDm2GYAAAAJcEhZcwAAFiUAABYlAUlSJPAAAAAZdEVYdFNvZnR3YXJlAE1pY3Jvc29mdCBPZmZpY2V/7TVxAAAAVklEQVQYV2NgoDrYAjSRdxmQWOjAwHBTDcjgEmHgnZgAsmihw00xsIVcwhMDIDYvFIW6YKIIhMEpPBGoEQgmOnCC5bhEgdpBqhcCCbD+oyArKqD6yKYAy6IOoPs7qsEAAAAASUVORK5CYII=\" alt=\"image\"\u003e\u0026nbsp;10\u003csup\u003e-24\u003c/sup\u003e esu. Conjugating with AgNCs significantly enhances polarizability, in all lycopene@Ag\u003csub\u003en\u003c/sub\u003e conjugates. The polarizability (𝛼\u003csub\u003e0\u003c/sub\u003e) values for lycopene@Ag\u003csub\u003e4\u003c/sub\u003eNC, lycopene@Ag\u003csub\u003e8\u003c/sub\u003eNC and lycopene@Ag\u003csub\u003e18\u003c/sub\u003eNC are 206.54\u0026nbsp;\u003cimg width=\"11\" height=\"19\" src=\"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAABAAAAAcBAMAAACaHyIpAAAAAXNSR0IArs4c6QAAACpQTFRFAAAAAAAAAAA6OpC2OpDbZrbbZrb/kDo6kNv/tmYAtmY625A625Bm///b97lStQAAAAF0Uk5TAEDm2GYAAAAJcEhZcwAAFiUAABYlAUlSJPAAAAAZdEVYdFNvZnR3YXJlAE1pY3Jvc29mdCBPZmZpY2V/7TVxAAAAVklEQVQYV2NgoDrYAjSRdxmQWOjAwHBTDcjgEmHgnZgAsmihw00xsIVcwhMDIDYvFIW6YKIIhMEpPBGoEQgmOnCC5bhEgdpBqhcCCbD+oyArKqD6yKYAy6IOoPs7qsEAAAAASUVORK5CYII=\" alt=\"image\"\u003e\u0026nbsp;10\u003csup\u003e-24\u003c/sup\u003e esu, 230.21\u0026nbsp;\u003cimg width=\"11\" height=\"19\" src=\"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAABAAAAAcBAMAAACaHyIpAAAAAXNSR0IArs4c6QAAACpQTFRFAAAAAAAAAAA6OpC2OpDbZrbbZrb/kDo6kNv/tmYAtmY625A625Bm///b97lStQAAAAF0Uk5TAEDm2GYAAAAJcEhZcwAAFiUAABYlAUlSJPAAAAAZdEVYdFNvZnR3YXJlAE1pY3Jvc29mdCBPZmZpY2V/7TVxAAAAVklEQVQYV2NgoDrYAjSRdxmQWOjAwHBTDcjgEmHgnZgAsmihw00xsIVcwhMDIDYvFIW6YKIIhMEpPBGoEQgmOnCC5bhEgdpBqhcCCbD+oyArKqD6yKYAy6IOoPs7qsEAAAAASUVORK5CYII=\" alt=\"image\"\u003e\u0026nbsp;10\u003csup\u003e-24\u003c/sup\u003e esu, and 286.94\u0026nbsp;\u003cimg width=\"11\" height=\"19\" src=\"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAABAAAAAcBAMAAACaHyIpAAAAAXNSR0IArs4c6QAAACpQTFRFAAAAAAAAAAA6OpC2OpDbZrbbZrb/kDo6kNv/tmYAtmY625A625Bm///b97lStQAAAAF0Uk5TAEDm2GYAAAAJcEhZcwAAFiUAABYlAUlSJPAAAAAZdEVYdFNvZnR3YXJlAE1pY3Jvc29mdCBPZmZpY2V/7TVxAAAAVklEQVQYV2NgoDrYAjSRdxmQWOjAwHBTDcjgEmHgnZgAsmihw00xsIVcwhMDIDYvFIW6YKIIhMEpPBGoEQgmOnCC5bhEgdpBqhcCCbD+oyArKqD6yKYAy6IOoPs7qsEAAAAASUVORK5CYII=\" alt=\"image\"\u003e\u0026nbsp;10\u003csup\u003e-24\u003c/sup\u003e esu, respectively. Compared to lycopene as a reference the lycopene@Ag\u003csub\u003e18\u003c/sub\u003e indicates the highest polarizability (𝛼\u003csub\u003e0\u003c/sub\u003e).\u003c/p\u003e\n\u003cp\u003eThe first-order hyperpolarizability (β\u003csub\u003e0\u003c/sub\u003e) for pure lycopene is 10.73\u0026nbsp;\u003cimg width=\"11\" height=\"19\" src=\"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAABAAAAAcBAMAAACaHyIpAAAAAXNSR0IArs4c6QAAACpQTFRFAAAAAAAAAAA6OpC2OpDbZrbbZrb/kDo6kNv/tmYAtmY625A625Bm///b97lStQAAAAF0Uk5TAEDm2GYAAAAJcEhZcwAAFiUAABYlAUlSJPAAAAAZdEVYdFNvZnR3YXJlAE1pY3Jvc29mdCBPZmZpY2V/7TVxAAAAVklEQVQYV2NgoDrYAjSRdxmQWOjAwHBTDcjgEmHgnZgAsmihw00xsIVcwhMDIDYvFIW6YKIIhMEpPBGoEQgmOnCC5bhEgdpBqhcCCbD+oyArKqD6yKYAy6IOoPs7qsEAAAAASUVORK5CYII=\" alt=\"image\"\u003e\u0026nbsp;10\u003csup\u003e-30\u003c/sup\u003e esu. However, a significant change in β\u003csub\u003e0\u003c/sub\u003e is observed in the lycopene@Ag\u003csub\u003en\u003c/sub\u003e conjugates. Lycopene@Ag\u003csub\u003e18\u003c/sub\u003eNC indicates the highest value (209.67\u0026nbsp;\u003cimg width=\"11\" height=\"19\" src=\"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAABAAAAAcBAMAAACaHyIpAAAAAXNSR0IArs4c6QAAACpQTFRFAAAAAAAAAAA6OpC2OpDbZrbbZrb/kDo6kNv/tmYAtmY625A625Bm///b97lStQAAAAF0Uk5TAEDm2GYAAAAJcEhZcwAAFiUAABYlAUlSJPAAAAAZdEVYdFNvZnR3YXJlAE1pY3Jvc29mdCBPZmZpY2V/7TVxAAAAVklEQVQYV2NgoDrYAjSRdxmQWOjAwHBTDcjgEmHgnZgAsmihw00xsIVcwhMDIDYvFIW6YKIIhMEpPBGoEQgmOnCC5bhEgdpBqhcCCbD+oyArKqD6yKYAy6IOoPs7qsEAAAAASUVORK5CYII=\" alt=\"image\"\u003e\u0026nbsp;10\u003csup\u003e-30\u003c/sup\u003e esu) than all other complexes. The study found that as the size of the nanoclusters increased, the β\u003csub\u003e0\u003c/sub\u003e also increased linearly in the order of Ag\u003csub\u003e4\u003c/sub\u003eNC \u0026lt; Ag\u003csub\u003e8\u003c/sub\u003eNC \u0026lt; Ag\u003csub\u003e18\u003c/sub\u003eNC. The overall increasing order for β\u003csub\u003e0\u0026nbsp;\u003c/sub\u003evalue is Lycopene \u0026lt; lycopene@Ag\u003csub\u003e4\u003c/sub\u003eNC \u0026lt; lycopene@Ag\u003csub\u003e8\u003c/sub\u003eNC \u0026lt; lycopene@Ag\u003csub\u003e18\u003c/sub\u003eNC.\u003c/p\u003e\n\u003cp\u003eIn second-order hyperpolarizability (𝛾),\u0026nbsp;lycopene@Ag\u003csub\u003e18\u003c/sub\u003e indicates the highest values (189.16\u0026nbsp;\u003cimg width=\"11\" height=\"19\" src=\"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAABAAAAAcBAMAAACaHyIpAAAAAXNSR0IArs4c6QAAACpQTFRFAAAAAAAAAAA6OpC2OpDbZrbbZrb/kDo6kNv/tmYAtmY625A625Bm///b97lStQAAAAF0Uk5TAEDm2GYAAAAJcEhZcwAAFiUAABYlAUlSJPAAAAAZdEVYdFNvZnR3YXJlAE1pY3Jvc29mdCBPZmZpY2V/7TVxAAAAVklEQVQYV2NgoDrYAjSRdxmQWOjAwHBTDcjgEmHgnZgAsmihw00xsIVcwhMDIDYvFIW6YKIIhMEpPBGoEQgmOnCC5bhEgdpBqhcCCbD+oyArKqD6yKYAy6IOoPs7qsEAAAAASUVORK5CYII=\" alt=\"image\"\u003e\u0026nbsp;10\u003csup\u003e-34\u003c/sup\u003e esu) to other lycopene@Ag\u003csub\u003en\u003c/sub\u003e conjugates. Therefore, the large values of 𝛾\u0026nbsp;permit us to conclude that these complexes have excellent linear and nonlinear optical properties and hence can be used in third-order nonlinear optical materials, which may have optoelectronic, photonic, and photodynamic therapy applications.\u003c/p\u003e\n\u003cp\u003eThe second-order nonlinearity can be obtained by combining two properties: the product of dipole moment (𝜇) and first-order hyperpolarizability (β\u003csub\u003e0\u003c/sub\u003e)\u0026nbsp;\u003csup\u003e50\u003c/sup\u003e. From\u0026nbsp;\u003cstrong\u003eTable 3\u003c/strong\u003e one can observe that compared to pure lycopene, larger values of\u0026nbsp;𝜇\u0026nbsp;β\u003csub\u003e0\u0026nbsp;\u003c/sub\u003eare obtained for lycopene@Ag\u003csub\u003e4\u003c/sub\u003e, lycopene@Ag\u003csub\u003e8\u003c/sub\u003e, and lycopene@Ag\u003csub\u003e18\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003eFrequency-dependent calculations were performed to evaluate the nonlinear response of the material at the operating wavelength during laser excitation for a particular device application \u003csup\u003e51\u003c/sup\u003e. Second harmonic generation (SHG), electro-optical Pockel’s effect (EOPE), electric field-induced second harmonic generation (ESHG) and the dc-Kerr effect were studied at 1064 nm, 532 nm, and the wavelength of the Nd:YAG laser \u003csup\u003e52\u003c/sup\u003e. Hence, the hyperpolarizability coefficients for SHG β(-2𝜔;\u0026nbsp;𝜔,\u0026nbsp;𝜔), EOPE β(-𝜔;\u0026nbsp;𝜔, 0), ESHG\u0026nbsp;𝛾(-2𝜔;\u0026nbsp;𝜔,\u0026nbsp;𝜔, 0), and dc-Kerr effect\u0026nbsp;𝛾(-𝜔;\u0026nbsp;𝜔, 0, 0) were calculated at 1064nm and 532 nm wavelength in B3LYP functional. The second- and third-order NLO coefficients for lycopene and lycopene@Ag\u003csub\u003en\u003c/sub\u003eNCs are listed in\u0026nbsp;\u003cstrong\u003eTable 4\u003c/strong\u003e and\u0026nbsp;\u003cstrong\u003eTable 5\u003c/strong\u003e, respectively.\u003c/p\u003e\n\u003cp\u003eThe SHG and EOPE values at 532 nm were higher than the values at 1064 nm for all the investigated compounds. Among these compounds, lycopene@Ag\u003csub\u003e18\u003c/sub\u003e demonstrated the highest SHG and EOPE; see \u003cstrong\u003eTable 4\u003c/strong\u003e. From \u003cstrong\u003eTable 5\u003c/strong\u003e, lycopene@Ag\u003csub\u003e18\u003c/sub\u003e showed larger dc-Kerr effect and ESHG values, and their values at 532 nm were higher than those at 1064 nm. Therefore, for both second- and third-order NLO coefficients, the values at 532 nm were higher than the values at 1064 nm for the studied compounds. From these results, we conclude that the dc-Kerr effect is the significant third-order NLO effect in lycopene and lycopene@Ag\u003csub\u003en\u003c/sub\u003e at 532 nm. This model can be used to predict the NLO effect of the material and the frequency of the laser at which the NLO coefficients would be wider.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eQuantitative molecular electrostatic potential (MEP) and difference density analysis\u003c/strong\u003e. The MEP descriptor is usually used to analyse charge transfer efficiency, soft-soft and hard-hard interaction, and the distribution of charge density among the complexes \u003csup\u003e49\u003c/sup\u003e.\u0026nbsp;\u003cstrong\u003eFigure 7\u003c/strong\u003e\u003cstrong\u003ea\u003c/strong\u003e displays the MEP maps of all the analysed components. Lycopene’s MEP is dominated by red along the linear carbon chain of the molecule, which represents the negative value of the electron density, thus making it more electrophilic. The electron density distribution in lycopene also revealed the red-hued zone at the two opposite ends of the molecule located in the two unconjugated C-C double bonds. These regions are very rich in electrons and can donate electron density to the orbitals of Ag atoms in the cluster. Based on our findings, the Ag clusters were bonded with lycopene in that specific region. Therefore, the region containing the AgNCs dopant and the backbone chain of lycopene is blue (positive value) and acts as nucleophiles. For the difference density, the blue region represents the positive value of the difference density, i.e., where the excited state density is larger than the ground state density. The red region indicates the reverse. Therefore, for lycopene, electron density moves from the region of the C-C double bonds to the region of the C-C single bonds as it transitions from the ground state to the first excited state; see\u0026nbsp;\u003cstrong\u003eFigure 7\u003c/strong\u003e\u003cstrong\u003eb\u003c/strong\u003e.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn the present work, we have demonstrated the enhancement of linear and NLO properties of lycopene bioconjugated silver nanoparticles. The absorbance intensity and the Raman intensity of the lycopene@Ag system substantially increased due to the improved excitation rate of silver nanoparticles. The TEM image showed that the pulsed laser ablation of a silver target in lycopene solution generated stable AgNPs with an average size of 16.53 nm. In the computational model, the lycopene@AgNCs interaction was studied. As silver models, the Ag\u003csub\u003e4\u003c/sub\u003e, Ag\u003csub\u003e8\u003c/sub\u003e and Ag\u003csub\u003e18\u003c/sub\u003e were proposed to investigate their linear and NLO properties. After performing the MEP of lycopene, the AgNCs were placed at the most electrophilic region of the molecule, which acts as the most stable binding site. The vertical excitation values were found to be closer to the experimental absorption maxima. The calculated\u0026nbsp;𝛼\u003csub\u003e0\u003c/sub\u003e, β\u003csub\u003e0\u003c/sub\u003e, and\u0026nbsp;𝛾\u003csub\u003e0\u003c/sub\u003e values of lycopene@AgNCs increased compared to lycopene and improved with the increasing size of the AgNCs. From the Frequency-dependent NLO properties at 1064 nm and 532 nm wavelength, it was observed that various second- and third-order NLO parameters, such as SHG β(-2𝜔;\u0026nbsp;𝜔,\u0026nbsp;𝜔), EOPE β(-𝜔;\u0026nbsp;𝜔, 0), and ESHG\u0026nbsp;𝛾(-2𝜔;\u0026nbsp;𝜔,\u0026nbsp;𝜔, 0), and dc-Kerr effect\u0026nbsp;𝛾(-𝜔;\u0026nbsp;𝜔, 0, 0), respectively, of lycopene@AgNCs also improved with the size of the AgNCs. Therefore, the dc-Kerr effect is the major third-order NLO effect in lycopene and lycopene@Ag\u003csub\u003en\u003c/sub\u003e at 532 nm. For the understanding of the third-order NLO effect related to the third-order NLO susceptibility, future deeper investigations are needed toward the Z-scan analysis technique.\u0026nbsp;\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eWe are grateful to the various supporting institutions, including the University of South Africa, iThemba LABS (ITLABS), the National Research Foundation of South Africa (NRF), the African Laser Centre (ALC), the international Organization of Women in Science (OWSD), the Abdus Salam International Centre for Theoretical Physics (The Abdus Salam-ICTP), the Royal Society-London \u0026nbsp;and naturally the United Nations Education, Sciences \u0026amp; Culture Organization (UNESCO) as well as the French Foreign Ministry and the ADESFA program. Likewise, the Centre for High Performance Computation (CHPC) is acknowledged. The first author gratefully acknowledges the support from Triangle Science, Education \u0026amp; Economic Development, LLC (TriSEED Consultant, LLC).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eE. L. T. N.: Conceptualisation, methodology, sample preparation, Modelling \u0026amp; computational studies, Data analysis, Writing original draft. N. M. M.: Sample synthesis \u0026amp; characterisation, review and editing. M. N. H.: Supervision, Review of the manuscript. M. M.: Conceptualisation, Supervision, Review \u0026amp; editing.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration of competing interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eData are available from the corresponding authors upon reasonable request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eSvechkarev, D. \u0026amp; Mohs, A. M. Organic Fluorescent Dye-based Nanomaterials: Advances in the Rational Design for Imaging and Sensing Applications. \u003cem\u003eCurr. Med. Chem.\u003c/em\u003e \u003cstrong\u003e26\u003c/strong\u003e, 4042\u0026ndash;4064 (2019).\u003c/li\u003e\n \u003cli\u003eYang, C.-C. \u003cem\u003eet al.\u003c/em\u003e Carbon based Y-type molecules for application in nonlinear optics. \u003cem\u003eJ. Mater. Chem. 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Med.\u003c/em\u003e \u003cstrong\u003e53\u003c/strong\u003e, 1158\u0026ndash;1165 (2021).\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Tables","content":"\u003cp\u003eTables 1 to 5 are available in the Supplementary Files section\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"Lycopene, Silver nanoparticles, In-situ bioconjugation, Nonlinear optical properties, Density functional theory","lastPublishedDoi":"10.21203/rs.3.rs-6498356/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6498356/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe synthesis of lycopene@silver nanoparticle bioconjugates by pulsed laser ablation in liquid was studied. The ablation product was characterised by UV-Vis optical absorption, Raman spectroscopy and transmission electron microscopy (TEM). The experimental results were confirmed by the computational studies. Furthermore, to assess the influence of the surface plasmon on nonlinear optical (NLO) responses, in this work, we investigated the NLO properties of lycopene@silver systems using the density functional theory (DFT) approach at the B3LYP/6-311G/LANL2DZ level. In addition to molecular descriptors, the static and dynamic (at the working wavelength of the device, 1064 nm and 532 nm) polarizability (𝛼), first hyperpolarizability (β), and second hyperpolarizability (𝛾) were calculated. Compared to the lycopene molecule, results of the lycopene@Ag\u003csub\u003e18\u003c/sub\u003e system show increased values of +2.88 D, 115.86 x 10\u003csup\u003e-24\u003c/sup\u003e esu, 198.94 x 10\u003csup\u003e-30\u003c/sup\u003e esu, and 33.73 x 10\u003csup\u003e-34\u003c/sup\u003e esu, for 𝜇, 𝛼\u003csub\u003e0\u003c/sub\u003e, β\u003csub\u003e0\u003c/sub\u003e, and 𝛾\u003csub\u003e0\u003c/sub\u003e, respectively. We found that lycopene@Ag systems have enhanced NLO properties, allowing us to hypothesise that the lycopene@AgNPs with the increased size of the AgNPs might be suitable as third-order NLO materials with increased stability, high flexibility in molecular engineering, and flexible photonic devices. Bioconjugated lycopene with AgNPs enhances local field effects, boosting both linear and NLO attributes.\u003c/p\u003e","manuscriptTitle":"Surface plasmon enhanced linear and nonlinear optical properties of lycopene bioconjugated silver nanoparticles","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-05-07 09:13:30","doi":"10.21203/rs.3.rs-6498356/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-06-02T04:25:34+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-05-27T16:52:50+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-05-15T13:05:03+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-05-14T11:03:15+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"232250826996471023915952444978593601269","date":"2025-05-04T15:26:23+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"226415298630552689481954354568876394085","date":"2025-05-04T11:12:28+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"1737524166280082811189586543055758931","date":"2025-05-04T11:11:54+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"194645837101496382617076769410092629288","date":"2025-05-03T03:52:11+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-05-02T10:48:35+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-05-02T10:32:39+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2025-05-02T05:16:54+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-04-23T09:10:41+00:00","index":"","fulltext":""},{"type":"submitted","content":"Scientific Reports","date":"2025-04-23T09:09:33+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"9750c22c-05ae-4e1f-a37d-851d392b1788","owner":[],"postedDate":"May 7th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":48044254,"name":"Physical sciences/Engineering"},{"id":48044255,"name":"Physical sciences/Materials science"},{"id":48044256,"name":"Physical sciences/Mathematics and computing"},{"id":48044257,"name":"Physical sciences/Nanoscience and technology"},{"id":48044258,"name":"Physical sciences/Optics and photonics"},{"id":48044259,"name":"Physical sciences/Physics"}],"tags":[],"updatedAt":"2025-07-28T16:10:21+00:00","versionOfRecord":{"articleIdentity":"rs-6498356","link":"https://doi.org/10.1038/s41598-025-13103-2","journal":{"identity":"scientific-reports","isVorOnly":false,"title":"Scientific Reports"},"publishedOn":"2025-07-25 15:58:22","publishedOnDateReadable":"July 25th, 2025"},"versionCreatedAt":"2025-05-07 09:13:30","video":"","vorDoi":"10.1038/s41598-025-13103-2","vorDoiUrl":"https://doi.org/10.1038/s41598-025-13103-2","workflowStages":[]},"version":"v1","identity":"rs-6498356","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6498356","identity":"rs-6498356","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}