On the biocompatibility of graphene oxide towards vascular smooth muscle cells.

Graphene and its derivatives have shown fascinating potential in biomedical applications. However, the biocompatibility of graphene with vascular smooth muscle cells (VSMCs) and applications to vascular engineering have not been explored extensively. Using a rat aortic smooth muscle cell line, A7r5, as a VSMC model, we have explored the effects of graphene oxide (GO) on the growth and behaviours of VSMCs. Results demonstrated that GO had no obvious toxicity to VSMCs. Cells cultured on GO retained the expression of smooth muscle cell-specific markers CNN1, ACTA2 and SMTN, on both mRNA and protein levels. A wound healing assay demonstrated no effect of GO on cell migration. We also found that small-flaked GO favoured the proliferation of VSMCs, suggesting a potential of using surface chemistry or physical properties of GO to influence cell growth behaviour. These results provide insight into the suitability of GO as a scaffold for vascular tissue engineering.

Designing Peptide/Graphene Hybrid Hydrogels through Fine-Tuning of Molecular Interactions.

A recent strategy that has emerged for the design of increasingly functional hydrogels is the incorporation of nanofillers in order to exploit their specific properties to either modify the performance of the hydrogel or add functionality. The emergence of carbon nanomaterials in particular has provided great opportunity for the use of graphene derivatives (GDs) in biomedical applications. The key challenge when designing hybrid materials is the understanding of the molecular interactions between the matrix (peptide nanofibers) and the nanofiller (here GDs) and how these affect the final properties of the bulk material. For the purpose of this work, three gelling ß-sheet-forming, self-assembling peptides with varying physiochemical properties and five GDs with varying surface chemistries were chosen to formulate novel hybrid hydrogels. First the peptide hydrogels and the GDs were characterized; subsequently, the molecular interaction between peptides nanofibers and GDs were probed before formulating and mechanically characterizing the hybrid hydrogels. We show how the interplay between electrostatic interactions, which can be attractive or repulsive, and hydrophobic (and π-π in the case of peptide containing phenylalanine) interactions, which are always attractive, play a key role on the final properties of the hybrid hydrogels. The shear modulus of the hydrid hydrogels is shown to be related to the strength of fiber adhesion to the flakes, the overall hydrophobicity of the peptides, as well as the type of fibrillar network formed. Finally, the cytotoxicity of the hybrid hydrogel formed at pH 6 was also investigated by encapsulating and culturing human mesemchymal stem cells (hMSC) over 14 days. This work clearly shows how interactions between peptides and GDs can be used to tailor the mechanical properties of the resulting hydrogels, allowing the incorporation of GD nanofillers in a controlled way and opening the possibility to exploit their intrinsic properties to design novel hybrid peptide hydrogels for biomedical applications.

Probing hotspots of plasmon-enhanced Raman scattering by nanomanipulation of carbon nanotubes.

We present a two-step procedure to probe hotspots of plasmon-enhanced Raman scattering with carbon nanotubes (CNTs). Dielectrophoretic deposition places a small CNT bundle on top of a plasmonic Au nanodimer. After 'pre-characterizing' both the nanotubes and dimer structure, we subsequently use the tip of an atomic force microscope to push the bundle into the plasmonic hotspot located in the 25 nm wide dimer gap, characterize its location inside the gap, and observe the onset of plasmon-enhanced Raman scattering. Evidence for the activation of the CNT's double-resonant D-mode by the near-field of the plasmonic hotspot is discussed.

Plasmonic enhancement of SERS measured on molecules in carbon nanotubes.

We isolated the plasmonic contribution to surface-enhanced Raman scattering (SERS) and found it to be much stronger than expected. Organic dyes encapsulated in single-walled carbon nanotubes are ideal probes for quantifying plasmonic enhancement in a Raman experiment. The molecules are chemically protected through the nanotube wall and spatially isolated from the metal, which prevents enhancement by chemical means and through surface roughness. The tubes carry molecules into SERS hotspots, thereby defining molecular position and making it accessible for structural characterization with atomic-force and electron microscopy. We measured a SERS enhancement factor of 106 on α-sexithiophene (6T) molecules in the gap of a plasmonic nanodimer. This is two orders of magnitude stronger than predicted by the electromagnetic enhancement theory (104). We discuss various phenomena that may explain the discrepancy (including hybridization, static and dynamic charge transfer, surface roughness, uncertainties in molecular position and orientation), but found all of them lacking in enhancement for our probe system. We suggest that plasmonic enhancement in SERS is, in fact, much stronger than currently anticipated. We discuss novel approaches for treating SERS quantum mechanically that appear promising for predicting correct enhancement factors. Our findings have important consequences on the understanding of SERS as well as for designing and optimizing plasmonic substrates.

Graphene and water-based elastomers thin-film composites by dip-moulding.

Thin-film elastomers (elastic polymers) have a number of technologically significant applications ranging from sportswear to medical devices. In this work, we demonstrate that graphene can be used to reinforce 20 micron thin elastomer films, resulting in over 50% increase in elastic modulus at a very low loading of 0.1 wt%, while also increasing the elongation to failure. This loading is below the percolation threshold for electrical conductivity. We demonstrate composites with both graphene oxide and reduced graphene oxide, the reduction being undertaken in-situ or ex-situ using a biocompatible reducing agent in ascorbic acid. The ultrathin films were cast by dip moulding. The transparency of the elastomer films allows us to use optical microscopy image and confirm the uniform distribution as well as the conformation of the graphene flakes within the composite.

Plasmon-enhanced Raman scattering by carbon nanotubes optically coupled with near-field cavities.

We realize the coupling of carbon nanotubes as a one-dimensional model system to near-field cavities for plasmon-enhanced Raman scattering. Directed dielectrophoretic assembly places single-walled carbon nanotubes precisely into the gap of gold nanodimers. The plasmonic cavities enhance the Raman signal of a small nanotube bundle by a factor of 10(3). The enhanced signal arises exclusively from tube segments within the cavity as we confirm by spatially resolved Raman measurements. Through the energy and polarization of the excitation we address the extrinsic plasmonic and the intrinsic nanotube optical response independently. For all incident light polarizations, the nanotube Raman features arise from fully symmetric vibrations only. We find strong evidence that the signal enhancement depends on the orientation of the carbon nanotube relative to the cavity axis.

Optical-phonon resonances with saddle-point excitons in twisted-bilayer graphene.

Twisted-bilayer graphene (tBLG) exhibits van Hove singularities in the density of states that can be tuned by changing the twisting angle θ. A θ-defined tBLG has been produced and characterized with optical reflectivity and resonance Raman scattering. The θ-engineered optical response is shown to be consistent with persistent saddle-point excitons. Separate resonances with Stokes and anti-Stokes Raman scattering components can be achieved due to the sharpness of the two-dimensional saddle-point excitons, similar to what has been previously observed for one-dimensional carbon nanotubes. The excitation power dependence for the Stokes and anti-Stokes emissions indicate that the two processes are correlated and that they share the same phonon.

Polarized plasmonic enhancement by Au nanostructures probed through Raman scattering of suspended graphene.

We characterize plasmonic enhancement in a hotspot between two Au nanodisks using Raman scattering of graphene. Single layer graphene is suspended across the dimer cavity and provides an ideal two-dimensional test material for the local near-field distribution. We detect a Raman enhancement of the order of 10(3) originating from the cavity. Spatially resolved Raman measurements reveal a near-field localization one order of magnitude smaller than the wavelength of the excitation, which can be turned off by rotating the polarization of the excitation. The suspended graphene is under tensile strain. The resulting phonon mode softening allows for a clear identification of the enhanced signal compared to unperturbed graphene.

Charge transfer at junctions of a single layer of graphene and a metallic single walled carbon nanotube.

Junctions between a single walled carbon nanotube (SWNT) and a monolayer of graphene are fabricated and studied for the first time. A single layer graphene (SLG) sheet grown by chemical vapor deposition (CVD) is transferred onto a SiO2/Si wafer with aligned CVD-grown SWNTs. Raman spectroscopy is used to identify metallic-SWNT/SLG junctions, and a method for spectroscopic deconvolution of the overlapping G peaks of the SWNT and the SLG is reported, making use of the polarization dependence of the SWNT. A comparison of the Raman peak positions and intensities of the individual SWNT and graphene to those of the SWNT-graphene junction indicates an electron transfer of 1.12 × 10¹³ cm⁻² from the SWNT to the graphene. This direction of charge transfer is in agreement with the work functions of the SWNT and graphene. The compression of the SWNT by the graphene increases the broadening of the radial breathing mode (RBM) peak from 3.6 ± 0.3 to 4.6 ± 0.5 cm⁻¹ and of the G peak from 13 ± 1 to 18 ± 1 cm⁻¹, in reasonable agreement with molecular dynamics simulations. However, the RBM and G peak position shifts are primarily due to charge transfer with minimal contributions from strain. With this method, the ability to dope graphene with nanometer resolution is demonstrated.

Modeling Graphene-Polymer Heterostructure MEMS Membranes with the Föppl-von Kármán Equations.

Ultra-thin graphene-based membranes have shown significant promise for high-performance nano-electro-mechanical (NEMS) devices. The key challenge in the modeling of such membranes is that they often operate in deflection regimes where the assumptions or approximations of "pure bending" or "pure stretching" are not satisfied. We present a model of graphene-polymer heterostructure (GPH) NEMS membranes based on Föppl-von Kármán (FvK) equations which take into account both bending and stretching forces. The experimental GPH membrane shape obtained through atomic force microscopy topography mapping is compared to the inflation shapes predicted by FvK-based finite element method simulation, and they show excellent agreement with each other. When the GPH membranes are deflected under pressure in a capacitive pressure sensor configuration, the effectiveness of this model is further exemplified through accurately predicting the capacitance change of deflecting GPH membrane devices at varying pressures. This model serves as a powerful new tool in the design and development of graphene-based NEMS devices, being able to predict the performance of graphene NEMS devices or to aid in the design of device geometries to match required performances.

Anisotropic organization and microscopic manipulation of self-assembling synthetic porphyrin microrods that mimic chlorosomes: bacterial light-harvesting systems.

Being able to control in time and space the positioning, orientation, movement, and sense of rotation of nano- to microscale objects is currently an active research area in nanoscience, having diverse nanotechnological applications. In this paper, we demonstrate unprecedented control and maneuvering of rod-shaped or tubular nanostructures with high aspect ratios which are formed by self-assembling synthetic porphyrins. The self-assembly algorithm, encoded by appended chemical-recognition groups on the periphery of these porphyrins, is the same as the one operating for chlorosomal bacteriochlorophylls (BChl's). Chlorosomes, rod-shaped organelles with relatively long-range molecular order, are the most efficient naturally occurring light-harvesting systems. They are used by green photosynthetic bacteria to trap visible and infrared light of minute intensities even at great depths, e.g., 100 m below water surface or in volcanic vents in the absence of solar radiation. In contrast to most other natural light-harvesting systems, the chlorosomal antennae are devoid of a protein scaffold to orient the BChl's; thus, they are an attractive goal for mimicry by synthetic chemists, who are able to engineer more robust chromophores to self-assemble. Functional devices with environmentally friendly chromophores-which should be able to act as photosensitizers within hybrid solar cells, leading to high photon-to-current conversion efficiencies even under low illumination conditions-have yet to be fabricated. The orderly manner in which the BChl's and their synthetic counterparts self-assemble imparts strong diamagnetic and optical anisotropies and flow/shear characteristics to their nanostructured assemblies, allowing them to be manipulated by electrical, magnetic, or tribomechanical forces.

Acidic and basic self-assembling peptide and peptide-graphene oxide hydrogels: characterisation and effect on encapsulated nucleus pulposus cells.

Extracellular pH can have a profound effect on cell metabolism, gene and protein expression. Nucleus pulposus (NP) cells, for example, under acidic conditions accelerate the production of degradative enzymes and pro-inflammatory cytokines, leading ultimately to intervertebral disc degeneration, a major cause of back pain. Self-assembling peptide hydrogels constitute a well-established class of biomaterials that could be exploited as pH-tunable platform to investigate cell behaviour under normal and non-physiological pH. In this paper we formulated acidic (pH = 4) and basic (pH = 9) hydrogels, from the same octapeptide FEFKFEFK (F8) (F = phenyalanine, E = glutamic acid, K = lysine), to test the effect of non-physiological pH on encapsulated NP cells. Similarly, graphene oxide-containing F8 hydrogels (GO-F8) were formulated as stiffer analogues. Acidic and basic hydrogels showed peculiar morphologies and rheological properties, with all systems able to buffer within 30 minutes of exposure to cell culture media. NP cells seeded in acidic F8 hydrogels showed a more catabolic phenotype compared to basic hydrogels, with increased gene expression of degradative enzymes (MMP-3, ADAMTS-4), neurotrophic factors (NGF and BDNF) and NF-κB p65 phosphorylation. Acidic GO-F8 hydrogels also induced a catabolic response, although milder than basic counterparts and with the highest gene expression of characteristic NP-matrix components, aggrecan and collagen II. In all systems, the cellular response had a peak within 3 days of encapsulation, thereafter decreasing over 7 days, suggesting a 'transitory' effect of hydrogel pH on encapsulated cells. This work gives an insight on the effect of pH (and pH buffering) on encapsulated NP cells and offers new designs of low and high pH peptide hydrogels for 3D cell culture studies. STATEMENT OF SIGNIFICANCE: We have recently shown the potential of graphene oxide - self-assembling peptide hybrid hydrogels for NP cell culture and regeneration. Alongside cell carrier, self-assembling peptide hydrogels actually provide a versatile pH-tunable platform for biological studies. In this work we decided to explore the effect of non-physiological pH (and pH buffering) on encapsulated NP cells. Our approach allows the formulation of both acidic and basic hydrogels, starting from the same peptide sequence. We showed that the initial pH of the scaffold does not affect significantly cell response to encapsulation, but the presence of GO results in lower inflammatory levels and higher NP matrix protein production. This platform could be exploited to study the effect of pH on different cell types whose behaviour can be pH-dependent.

Mechanically Stable Ultrathin Layered Graphene Nanocomposites Alleviate Residual Interfacial Stresses: Implications for Nanoelectromechanical Systems.

Advanced nanoelectromechanical systems made from polymer dielectrics deposited onto 2D-nanomaterials such as graphene are increasingly popular as pressure and touch sensors, resonant sensors, and capacitive micromachined ultrasound transducers (CMUTs). However, durability and accuracy of layered nanocomposites depend on the mechanical stability of the interface between polymer and graphene layers. Here we used molecular dynamics computer simulations to investigate the interface between a sheet of graphene and a layer of parylene-C thermoplastic polymer during large numbers of high-frequency (MHz) cycles of bending relevant to the operating regime. We find that important interfacial sliding occurs almost immediately in usage conditions, resulting in more than 2% expansion of the membrane, a detrimental mechanism which requires repeated calibration to maintain CMUTs accuracy. This irreversible mechanism is caused by relaxation of residual internal stresses in the nanocomposite bilayer, leading to the emergence of self-equilibrated tension in the polymer and compression in the graphene. It arises as a result of deposition-polymerization processing conditions. Our findings demonstrate the need for particular care to be exercised in overcoming initial expansion. The selection of appropriate materials chemistry including low electrostatic interactions will also be key to their successful application as durable and reliable devices.

Imaging conduction pathways in carbon nanotube network transistors by voltage-contrast scanning electron microscopy.

The performance of field-effect transistors based on single-walled carbon nanotube (SWCNT) networks depends on the electrical percolation of semiconducting and metallic nanotube pathways within the network. We present voltage-contrast scanning electron microscopy (VC-SEM) as a new tool for imaging percolation in a SWCNT network with nano-scale resolution. Under external bias, the secondary-electron contrast of SWCNTs depends on their conductivity, and therefore it is possible to image the preferred conduction pathways within a network by following the contrast evolution under bias in a scanning electron microscope. The experimental VC-SEM results are correlated to percolation models of SWCNT-bundle networks.

Graphene and water-based elastomer nanocomposites - a review.

Water-based elastomers (WBEs) are polymeric elastomers in aqueous systems. WBEs have recently continued to gain wide acceptability by both academia and industry due to their remarkable environmental and occupational safety friendly nature, as a non-toxic elastomeric dispersion with low-to-zero volatile organic compound (VOC) emission. However, their inherent poor mechanical and thermal properties remain a drawback to these sets of elastomers. Hence, nano-fillers such as graphene oxide (GO), reduced graphene oxide (rGO) and graphene nanoplatelets (GNPs) are being employed for the reinforcement and enhancement of this set of elastomers. This work is geared towards a critical review and summation of the state-of-the-art developments of graphene enhanced water-based elastomer composites (G-WBEC), including graphene and composite production processes, properties, characterisation techniques and potential commercial applications. The dominant production techniques, such as emulsion mixing and in situ polymerisation processes, which include Pickering emulsion, mini-emulsion and micro-emulsion, as well as ball-milling approach, are systematically evaluated. Details of the account of mechanical properties, electrical conductivity, thermal stability and thermal conductivity enhancements, as well as multifunctional properties of G-WBEC are discussed, with further elaboration on the structure-property relationship effects (such as dispersion and filler-matrix interface) through effective and non-destructive characterisation tools like Raman and XRD, among others. The paper also evaluates details of the current application attempts and potential commercial opportunities for G-WBEC utilisation in aerospace, automotive, oil and gas, biomedicals, textiles, sensors, electronics, solar energy, and thermal management.

Development of an open-source thermally stabilized quartz crystal microbalance instrument for biomolecule-substrate binding assays on gold and graphene.

The interaction of biomolecules, such as proteins, with biomaterial surfaces is key to disease diagnostic and therapeutic development applications. There is a significant need for rapid, low-cost, field-serviceable instruments to monitor such interactions, where open-source tools can help to improve the accessibility to disease screening instruments especially in low- and middle-income countries. We have developed and evaluated a low-cost integrated quartz crystal microbalance (QCM) instrument for biomolecular analysis based on an open-source QCM device. The custom QCM instrument was equipped with a custom-made electronically controlled isothermal chamber with a closed-loop control routine. A thermal coefficient of 5.6 ppm/°C was obtained from a series of evaluations of the implemented control. Additionally, a custom-designed data acquisition system and a mathematical processing and analysis tool is implemented. The quartz crystal detection chips used here incorporate gold and reduced graphene oxide (rGO) coated surfaces. We demonstrate the system capability to monitor and record the biomolecular interaction between a typical protein bovine serum albumin (BSA) and these two substrates. This instrument was compared to a commercial QCM, demonstrating good correspondence between the computed mass adsorption density responses using the Sauerbrey model. For both Au and rGO surfaces, the custom QCM significantly outperforms the commercial system in limit of detection, sensitivity and linear range. The instrument presented here has the potential to serve as a ubiquitous bioelectronic tool for point-of-care disease screening and rapid therapeutics development.

Graphene Oxide Substrate Promotes Neurotrophic Factor Secretion and Survival of Human Schwann-Like Adipose Mesenchymal Stromal Cells.

Mesenchymal stromal cells from adipose tissue (AD-MSCs) exhibit favorable clinical traits for autologous transplantation and can develop 'Schwann-like' phenotypes (sAD-MSCs) to improve peripheral nerve regeneration, where severe injuries yield insufficient recovery. However, sAD-MSCs regress without biochemical stimulation and detach from conduits under unfavorable transplant conditions, negating their paracrine effects. Graphene-derived materials support AD-MSC attachment, regulating cell adhesion and function through physiochemistry and topography. Graphene oxide (GO) is a suitable substrate for human sAD-MSCs incubation toward severe peripheral nerve injuries by evaluating transcriptome changes, neurotrophic factor expression over a 7-days period, and cell viability in apoptotic conditions is reported. Transcriptome changes from GO incubation across four patients are minor compared to biological variance. Nerve growth factor (NGF), brain-derived neurotrophic factor (BDNF), and glial-derived neurotrophic factor (GDNF) gene expression is unchanged from sAD-MSCs on GO substrates, but NGF and GDNF protein secretion increase at day 3 and 7. Secretome changes do not improve dorsal root ganglia neuron axon regeneration in conditioned media culture models. Fewer sAD-MSCs detach from GO substrates compared to glass following phosphate buffer saline exposure, which simulates apoptotic conditions. Overall, GO substrates are compatible with sAD-MSC primed for peripheral nerve regeneration strategies and protect the cell population in harsh environments.

TGF-ß3-loaded graphene oxide - self-assembling peptide hybrid hydrogels as functional 3D scaffolds for the regeneration of the nucleus pulposus.

Intervertebral disc (IVD) degeneration is a process that starts in the central nucleus pulposus (NP) and leads to inflammation, extracellular matrix (ECM) degradation, and progressive loss of disc height. Early treatment of IVD degeneration is critical to the reduction of low back pain and related disability. As such, minimally invasive therapeutic approaches that can halt and reverse NP degeneration at the early stages of the disease are needed. Recently, we developed an injectable graphene oxide (GO) - self-assembling peptide FEFKFEFK (F: phenylalanine; K: lysine; E: glutamic acid) hybrid hydrogels as potential delivery platform for cells and/or drugs in the NP. In this current study, we explored the possibility of using the GO present in these hybrid hydrogels as a vehicle for the sequestration and controlled delivery of transforming growth factor beta-3 (TGF-ß3), an anabolic growth factor (GF) known to direct NP cell fate and function. For this purpose, we first investigated the potential of GO to bind and sequestrate TGF-ß3. We then cultured bovine NP cells in the new functional scaffolds and investigated their response to the presence of GO and TGF-ß3. Our results clearly showed that GO flakes can sequestrate TGF-ß3 through strong binding interactions resulting in a slow and prolonged release, with the GF remaining active even when bound to the GO flakes. The adsorption of the GF on the GO flakes to create TGF-ß3-loaded GO flakes and their subsequent incorporation in the hydrogels through mixing, [(GO/TGF-ß3Ads)-F8] hydrogel, led to the upregulation of NP-specific genes, accompanied by the production and deposition of an NP-like ECM, rich in aggrecan and collagen II. NP cells actively interacted with TGF-ß3-loaded GO flakes and remodeled the scaffolds through endocytosis. This work highlights the potential of using GO as a nanocarrier for the design of functional hybrid peptide-based hydrogels. STATEMENT OF SIGNIFICANCE: Intervertebral disc (IVD) degeneration is a process that starts in the central nucleus pulposus (NP) and leads to inflammation, extracellular matrix (ECM) degradation, and progressive loss of disc height. As such, minimally invasive therapeutic approaches that can halt and reverse NP degeneration at the early stages of the disease are needed. In this current study, we explored the possibility of using peptide - GO hybrid hydrogels as a vehicle for the sequestration and controlled delivery of transforming growth factor beta-3 (TGF-ß3), an anabolic growth factor (GF) known to direct NP cell fate and function.

A Point-of-Care Immunosensor Based on a Quartz Crystal Microbalance with Graphene Biointerface for Antibody Assay.

We present a sensitive and low-cost immunoassay, based on a customized open-source quartz crystal microbalance coupled with graphene biointerface sensors (G-QCM), to quantify antibodies in undiluted patient serum. We demonstrate its efficacy for a specific antibody against the phospholipase A2 receptor (anti-PLA2R), which is a biomarker in primary membranous nephropathy. A novel graphene-protein biointerface was constructed by adsorbing a low concentration of denatured bovine serum albumin (dBSA) on the reduced graphene oxide (rGO) sensor surface. The dBSA film prevents the denaturation of the protein receptor on the rGO surface and serves as the cross-linker for immobilization of the receptor for anti-PLA2R antibodies on the surface. The detection limit and selectivity of this G-QCM biosensor was compared with a commercial QCM system. The G-QCM immunoassay exhibited good specificity and high sensitivity toward the target, with an order of magnitude better detection limit (of 100 ng/mL) compared to the commercial system, at a fraction of the cost and with considerable time saving. The results obtained from patient sera compared favorably with those from enzyme-linked immunosorbent assay, validating the feasibility of use in clinical applications. The multifunctional dBSA-rGO platform provides a promising biofunctionalization method for universal immunoassay and biosensors. With the advantages of inexpensive, rapid, and sensitive detection, the G-QCM sensor and instrument form an effective autoimmune disease screening tool.

Resonant, Plasmonic Raman Enhancement of α-6T Molecules Encapsulated in Carbon Nanotubes.

Surface-enhanced Raman scattering (SERS) and resonant Raman scattering are widely used techniques to enhance the Raman intensity of molecules and nanomaterials by several orders of magnitude. In SERS, typically, molecules are investigated and their intrinsic resonance is often ignored while discussing the plasmonic enhancement. Here, we study α-sexithiophenes encapsulated in carbon nanotubes placed in the center of a nanodimer. By dielectrophoretic deposition, we place the nanotubes precisely in the center of a plasmonic gold nanodimer and observe SERS enhancement from individual tube bundles. The encapsulated molecules are not subjected to chemical enhancement because of the protective character of the nanotube. Polarization-dependent Raman measurements confirm the alignment of the molecules within the carbon nanotubes (CNTs) and reveal the influence of the plasmonic near field on the molecule's Raman intensity. We investigate the encapsulated molecules in small CNT bundles with and without plasmonic enhancement and determine the molecular and plasmonic resonance by tuning the excitation wavelength. We observe a strong red shift of the maximum Raman intensity under plasmonic enhancement toward the plasmon resonance.