Preparation of a nanocomposite film from poly(diallydimethyl ammonium chloride) and gold nanoparticles by in-situ electrochemical reduction, and its application to SERS spectroscopy and sensing of ascorbic acid

A nanocomposite film is described that is composed of alternating layers of poly(diallydimethyl ammonium chloride) and gold nanoparticles that interact through electrostatic forces. The films of varying thickness were prepared by the layer-by-layer technique, and Au-NPs were generated by electrochemical reduction of hexachloroauric acid. The composite films were characterized by UV?Cvis spectroscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry. Most nanocomposite films exhibit linear, uniform, and regular layer-by-layer growth during the process of formation. The films exhibit unique performance in terms of surface enhanced Raman scattering and electrocatalytic activitiy towards the oxidation of ascorbic acid.

Electrochemical approaches for the fabrication and/or characterization of pure and hybrid templated mesoporous oxide thin films: a review

Electrochemistry can be used for fabrication and characterization of mesoporous oxide films. First, this review provides insight into the methods used to prepare templated mesoporous thin films on an electrode surface, i.e., evaporation-induced self-assembly (EISA) and electrochemically assisted self-assembly (EASA). Electrochemical characterization of mass transport processes in pure and organically functionalized mesoporous oxide films is then discussed. The electrochemical response can be basically restricted by the electron/mass transfer reaction at the electrode–film interface and diffusion through mesopore channels. The contributions of cyclic voltammetry, hydrodynamic voltammetry, electrochemical impedance spectroscopy, and scanning electrochemical microscopy to the characterization of films with distinct mesostructures are finally described, with special emphasis on identification of conditions that can affect the electrochemical response recorded with such modified electrodes.

Moving-window two-dimensional correlation infrared spectroscopy study on structural variations of partially hydrolyzed poly(vinyl alcohol)

In the present study, the molecular chain changes and structural transitions of partially hydrolyzed poly(vinyl alcohol) (PVA) having a 12 mol% acetate unit were analyzed by moving-window two-dimensional (MW2D) correlation infrared spectroscopy combined with differential scanning calorimetry and thermogravimetric analysis. The results show the glass-transition temperature (T _g ) of PVA is clearly distinguished by MW2D correlation infrared spectroscopy, and the acetate groups start to be eliminated around the melting temperature, whereas the free water molecules in PVA are eliminated above T _g. The correlation movements of the O–H stretching modes, including the free hydroxyl groups and the hydrogen bonds, are clearly determined using MW2D correlation infrared spectroscopy. The spectral variations in the C=O stretching region caused by the elimination of the acetate unit from polymer chains are also discussed on the basis of the results of the MW2D correlation analysis. Such results cannot be obtained by traditional infrared spectroscopy owing to the complex overlapping peaks.

A surface plasmon resonance study on the optical properties of gold nanoparticles on thin gold films

We report on an investigation of the optical properties of gold nanoparticles assembled as thin films of different thickness. The nanoparticles were linked to the surface of a gold chip by dithiol reagents and studied by surface plasmon resonance (SPR) spectroscopy and atomic force microscopy. There is good correlation between the experimental findings and theoretical simulation, and the respective data reveal the presence of ordered nanostructures in the assemblies. The shift in the SPR angle is linearly dependent on the particle size and the ratio of the different particles. SPR spectroscopy also reveals important information in terms of the optical constants of such films. This shall be further applied to in-situ quality control in the fabrication of optoelectronic, solar cell and semiconductor devices.

Characterization and analysis of mycobacteria and Gram-negative bacteria and co-culture mixtures by Raman microspectroscopy, FTIR, and atomic force microscopy

The molecular composition of mycobacteria and Gram-negative bacteria cell walls is structurally different. In this work, Raman microspectroscopy was applied to discriminate mycobacteria and Gram-negative bacteria by assessing specific characteristic spectral features. Analysis of Raman spectra indicated that mycobacteria and Gram-negative bacteria exhibit different spectral patterns under our experimental conditions due to their different biochemical components. Fourier transform infrared (FTIR) spectroscopy, as a supplementary vibrational spectroscopy, was also applied to analyze the biochemical composition of the representative bacterial strains. As for co-cultured bacterial mixtures, the distribution of individual cell types was obtained by quantitative analysis of Raman and FTIR spectral images and the spectral contribution from each cell type was distinguished by direct classical least squares analysis. Coupled atomic force microscopy (AFM) and Raman microspectroscopy realized simultaneous measurements of topography and spectral images for the same sampled surface. This work demonstrated the feasibility of utilizing a combined Raman microspectroscopy, FTIR, and AFM techniques to effectively characterize spectroscopic fingerprints from bacterial Gram types and mixtures.

Microextraction by packed sorbents combined with surface-enhanced Raman spectroscopy for determination of musk ketone in river water

Microextraction by packed sorbents (MEPS) combined with Surface-enhanced Raman spectroscopy (SERS) was investigated, and applied to the determination of musk ketone (MK) in river water samples. The full MEPS–SERS method includes analyte enrichment by MEPS preconcentration with C₁₈ sorbent followed by SERS detection supported by silver nanoparticles. An eluent drop containing the analyte is deposited directly from the MEPS syringe on a CaF₂ glass plate. When the drop has dried, a specific volume of silver nanoparticles solution is added on it before each SERS measurement. Several experimental variables were studied in depth; under the optimum experimental conditions MK can be extracted from a 500 μL sample with recoveries in the range 47–63 %. The limit of detection was 0.02 mg L^?1 and the relative standard deviation 15.2 % (n?=?4). Although not investigated in this work, the proposed method might be suitable for in-situ monitoring, because of the portability of the Raman spectrometer used.

The complete replacement of antibodies by protein-imprinted poly(ethylene-co-vinyl alcohol) in sandwich fluoroimmunoassays

The replacement of antibodies by molecularly imprinted polymers (MIPs) has been investigated for many decades. However, indirect protocols (including natural primary and secondary antibodies) are still utilized to evaluate the ability of MIP thin films to recognize target molecules. MIPs can be prepared as either a thin film or as particles, and cavities that are complementary to the template can be generated on their surfaces. We have prepared thin film MIPs and particle MIPs prepared by solvent evaporation and phase inversion, respectively, from solutions of poly(ethylene-co-vinyl alcohol) (pEVAL) in the presence of the target analytes amylase, lysozyme, and lipase. These were first adsorbed on MIP thin films and by MIP particles that contain fluorescent quantum dots. Sandwich fluoroimmunoassays were then conducted to quantify them in MIP-coated 96-well microplates. The method was applied to determine amylase in saliva, and results were compared with a commercial analytical system.

Iron oxide film growth under ultrathin polysiloxane networks

This study focuses on the preparation and characterization of magnetic switchable thin iron oxide–polymer films. In a series of experiments, the formation and growth of iron oxide under ultrathin polysiloxane layers was controlled by changing the concentration of iron ions in the aqueous subphase or by varying the residence time of ammonia in the gas phase above the liquid sample. The growth of the combined film structures is studied in situ by interfacial rheology, optical microscopy, and x-ray scattering experiments and ex situ by scanning electron microscopy. Different stages of iron oxide aggregation, from a very thin layer of amorphous iron oxide with thickness of a few nanometers up to micrometer thick coatings of crystalline maghemite (γ-Fe₂O₃) were investigated. The specific interactions between the inorganic iron oxide and the polymer membranes cause the creation of new composite materials which are sensitive to magnetic forces.

Patterned growth of vertically aligned silicon nanowire arrays for label-free DNA detection using surface-enhanced Raman spectroscopy

Patterning is of paramount importance in many areas of modern science and technology. As a good candidate for novel nanoscale optoelectronics and miniaturized molecule sensors, vertically aligned silicon nanowire (SiNW) with controllable location and orientation is highly desirable. In this study, we developed an effective procedure for the fabrication of vertically aligned SiNW arrays with micro-sized features by using single-step photolithography and silver nanoparticle-induced chemical etching at room temperature. We demonstrated that the vertically aligned SiNW arrays can be used as a platform for label-free DNA detection using surface-enhanced Raman spectroscopy (SERS), where the inherent “fingerprint” SERS spectra allows for the differentiation of closely related biospecies. Since the SiNW array patterns could be modified by simply varying the mask used in the photolithographic processing, it is expected that the methodology can be used to fabricate label-free DNA microarrays and may be applicable to tissue engineering, which aims to create living tissue substitutes from cells seeded onto 3D scaffolds.

Coating sulfonated polystyrene microspheres with highly dense gold nanoparticle shell for SERS application

The fabrication of highly dense gold nanoparticles (NPs)-coated sulfonated polystyrene (PS) microspheres and their application in surface-enhanced Raman spectroscopy (SERS) were reported. After the preparation of PS microsphere using dispersion polymerization and subsequent sulfonation, [Ag(NH₃)₂]⁺ ions were adsorbed on the surfaces of the sulfonated PS microspheres and then reduced to silver nanoseeds for further growth of gold NPs shell by seeded growth approach. Reaction conditions such as the concentration of the growth solution and growth time were adjusted to achieve nonspherical gold NPs-coated PS microspheres with different coverage degree. The application of the as-prepared spiky gold NPs-coated PS microsphere hybrid composite in SERS was finally investigated by using 4-aminothiophenol as probe molecules. The results showed that as-prepared gold NPs-coated PS microspheres could be used as functional hybrid materials to exhibit excellent enhancement ability in SERS.

Quantitative Raman spectroscopy in turbid matter: reflection or transmission mode?

Raman intensities from reflection (X _R ) and transmission (X _T ) setups are compared by calculations based on random walk and analytical approaches with respect to sample thickness, absorption, and scattering. Experiments incorporating strongly scattering organic polymer layers and powder tablets of pharmaceutical ingredients validate the theoretical findings. For nonabsorbing layers, the Raman reflection and transmission intensities rise steadily with the layer thickness, starting for very thin layers with the ratio X _T /X _R ?=?1 and approaching for thick layers, a lower limit of X _T /X _R ?=?0.5. This result is completely different from the primary irradiation where the ratio of transmittance/reflectance decays hyperbolically with the layer thickness to zero. In absorbing materials, X _R saturates at levels that depend strongly on the absorption and scattering coefficients. X _T passes through a maximum and decreases then exponentially with increasing layer thickness to zero. From the calculated radial intensity spreads, it follows that quantitative transmission Raman spectroscopy requires diameters of the detected sample areas be about six times larger than the sample thickness. In stratified systems, Raman transmission allows deep probing even of small quantities in buried layers. In double layers, the information is independent from the side of the measurements. In triple layers simulating coated tablets, the information of X _T originates mainly from the center of the bulk material whereas X _R highlights the irradiated boundary region. However, if the stratified sample is measured in a Raman reflection setup in front of a white diffusely reflecting surface, it is possible to monitor the whole depth of a multiple scattering sample with equal statistical weight. This may be a favorable approach for inline Raman spectroscopy in process analytical technology.

New strategies for the chemical characterization of multi-walled carbon nanotubes and their derivatives

Industrially relevant characterization of multi-walled carbon nanotubes (MWCNT) is still a challenging task. The aim of this work is to show novel and fast concepts for the chemical characterization of carbon nanotubes (CNT) by a combination of analytical techniques. Information obtained by individual tools like Fourier transform infrared spectroscopy (FTIR), attenuated total reflection infrared spectroscopy or Raman spectroscopy is not providing a full picture of the functionalization of MWCNTs. However, a combination of tools such as FTIR or mass spectrometry with thermogravimetric methods proved to be very useful. Sample preparation for FTIR and Raman spectroscopy is another focus of this contribution because of its strong effect on the results obtained. We also are suggesting methods for sample preparation that lead to highly reproducibility results. Measurements have been carried out on typical CNT samples such as commercially available pristine, carboxylated and amino-functionalized MWCNTs, and on polystyrenegrafted MWCNTs. The results may serve as a guidance for the qualitative and quantitative characterization of CNT.

A simple strategy for detecting synthetic polymers on solid surfaces using liquid crystal

In this study, we developed a liquid crystal (LC)-based detection method for polymer films synthesized on solid surfaces. A dark to bright transition in the optical appearance of nematic 4-cyano-4′-pentylbiphenyl (5CB) was observed after transferring a poly(methyl methacrylate) (PMMA) film onto a glass substrate functionalized with n-octyltrichlorosilane (OTS). This phenomenon indicates an orientational transition of 5CB from a homeotropic to a planar-random state. The optical response of 5CB was then evaluated directly through polymerization reactions on the OTS-functionalized glass substrate. Polymer films of PMMA, poly(glycidyl methacrylate) (PGMA), and poly(dimethylsiloxane) (PDMS) were synthesized on OTS surfaces covered with their reaction mixtures. All polymer films displayed bright signals of 5CB, which corresponded to the planar-random orientation of LCs. However, no change in orientation was observed for the control experiments. We confirmed the formation of polymer films on the OTS surface using atomic force microscopy. Overall, our results suggest that LCs can be used to construct optical monitoring systems for the product of polymerization reactions.

Recent progress in surface enhanced Raman spectroscopy for the detection of environmental pollutants

Surface enhanced Raman spectroscopy (SERS) has emerged as one of the most promising analytical tools in recent years. Due to advantageous features such as sensitivity, specificity, ease of operation and rapidity, SERS is particularly well suited for environmental analysis. We summarize here some considerations with respect to the detection of pollutants by SERS and provide an overview on recent achievements in the determination of organic pollutants, heavy metal ions, and pathogens. Following an introduction into the topic and considering aspects of sensitivity, selectivity, reproducibility and portability, we are summarizing applications of SERS in the detection of pollutants, with sections on organic pollutants (pesticides, PAHs and PCBs, explosives), on heavy metal ions, and on pathogens. In addition, we discuss current challenges and give an outlook on applications of SERS in environmental analysis. Contains 174 references.

Microfluidic channel with embedded SERS 2D platform for the aptamer detection of ochratoxin A

A selective aptameric sequence is adsorbed on a two-dimensional nanostructured metallic platform optimized for surface-enhanced Raman spectroscopy (SERS) measurements. Using nanofabrication methods, a metallic nanostructure was prepared by electron-beam lithography onto a glass coverslip surface and embedded within a microfluidic channel made of polydimethylsiloxane, allowing one to monitor in situ SERS fingerprint spectra from the adsorbed molecules on the metallic nanostructures. The gold structure was designed so that its localized surface plasmon resonance matches the excitation wavelength used for the Raman measurement. This optofluidic device is then used to detect the presence of a toxin, namely ochratoxin-A (OTA), in a confined environment, using very small amounts of chemicals, and short data acquisition times, by taking advantage of the optical properties of a SERS platform to magnify the Raman signals of the aptameric monolayer system and avoiding chemical labeling of the aptamer or the OTA target.

Hydrogen peroxide sensor based on a stainless steel electrode coated with multi-walled carbon nanotubes modified with magnetite nanoparticles

Multi-walled carbon nanotubes (MWCNTs) were decorated with magnetite (Fe₃O₄) nanoparticles and then used to modify a stainless steel electrode. The Fe₃O₄/MWCNTs composite was characterized by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and X-ray diffraction patterns. Electrochemical properties of the modified electrode revealed a substantial catalytic activity for the reduction of hydrogen peroxide. The relationship between peak current and the concentration of hydrogen peroxide was linear in the range from 0.06?mmol?L^?1 to 0.36?mmol?L^?1, and the lowest detectable concentration is 0.01?mmol·L^?1 (S/N?=?3). The modified stainless steel electrode displays excellent stability.

One-pot solvothermal synthesis of a Cu2O/Graphene nanocomposite and its application in an electrochemical sensor for dopamine

Nanocomposites composed of cuprous oxide (Cu₂O) and graphene were synthesized via reduction of copper(II) in ethylene glycol. This material possesses the specific features of both Cu₂O and graphene. Its morphology was characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy. Cyclic voltammetry was used to evaluate the electrochemical response of a glass carbon electrode (GCE) modified with the nanocomposite towards dopamine (DA). Compared to the bare GCE, the Cu₂O nanoparticles modified electrode and the graphene modified electrode, the nanocomposites modified electrode displays high electrocatalytic activity in giving an oxidation peak current that is proportional to the concentration of DA in the range from 0.1 to 10???M,with a detection limit of 10?nM (S/N?=?3). The modified electrode shows excellent selectivity and sensitivity even in the presence of high concentration of uric acid and can be applied to determine DA in real samples with satisfactory results.

Angle-dependent resonance of localized and propagating surface plasmons in microhole arrays for enhanced biosensing

The presence of microhole arrays in thin Au films is suited for the excitation of localized and propagating surface plasmon (SP) modes. Conditions can be established to excite a resonance between the localized and propagating SP modes, which further enhanced the local electromagnetic (EM) field. The co-excitation of localized and propagating SP modes depends on the angle of incidence (θ _exc) and refractive index of the solution interrogated. As a consequence of the enhanced EM field, enhanced sensitivity and an improved response for binding events by about a factor of 3 to 5 was observed with SPR sensors in the Kretschmann configuration for a set of experimental conditions (λ _SPR, θ _exc, and η). Thus, microhole arrays can improve sensing applications of SPR based on classical prism-based instrumentation and are suited for SP-coupled spectroscopic techniques.

Correlation between wetting properties and electrical performance of solution processed PEDOT:PSS/CNT nano-composite thin films

Nano-composite thin films of poly(3,4-ethylenedioxythiophene) poly(styrene-sulfonate) (PEDOT:PSS) with different loading concentrations of multi-walled carbon nanotubes (MWCNT) were deposited on glass substrates using inkjet printing and spin coating techniques. The surface energy of the substrate was modified using an oxygen plasma to achieve different degrees of wetting by the composite solution. We show that the electrical properties strongly depend on the wetting of the substrate and by controlling the wettability, the conductivity of the nano-composite samples can be improved. Based on polymer conductivity, the electrical conductivity of the composite film can be improved or degraded by orders of magnitude with the incorporation of the same concentration of MWCNT. Moreover, electrical measurements show strong correlation between the conductivity of the carbon nanotube network and the resulting nano-composite films. The dependence of electrical properties on the wettability and the conductivity of the composite components could explain the diversity in the electrical behaviour reported in the literature for PEDOT:PSS/MWCNT nano-composite thin films.

Spectroscopic detection and quantification of heme and heme degradation products

Heme and heme degradation products play critical roles in numerous biological phenomena which until now have only been partially understood. One reason for this is the very low concentrations at which free heme, its complexes and the partly unstable degradation products occur in living cells. Therefore, powerful and specific detection methods are needed. In this contribution, the potential of nondestructive Raman spectroscopy for the detection, quantification and discrimination of heme and heme degradation products is investigated. Resonance Raman spectroscopy using different excitation wavelengths (413, 476, 532, and 752?nm) is employed to estimate the limit of detection for hemin, myoglobin, biliverdin, and bilirubin. Concentrations in the low micromolar range (down to 3?μmol/L) could be reliably detected when utilizing the resonance enhancement effect. Furthermore, a systematic study on the surface-enhanced Raman spectroscopy (SERS) detection of hemin in the presence of other cellular components, such as the highly similar cytochrome c, DNA, and the important antioxidant glutathione, is presented. A microfluidic device was used to reproducibly create a segmented flow of aqueous droplets and oil compartments. Those aqueous droplets acted as model chambers where the analytes have to compete for the colloid. With the help of statistical analysis, it was possible to detect and differentiate the pure substances as well as the binary mixtures and gain insights into their interaction.