Spectroscopic studies of large sheets of graphene oxide and reduced graphene oxide monolayers prepared by Langmuir-Blodgett technique

Graphene oxide (GO) sheets prepared by chemical exfoliation were spread at the air-water interface and transferred to silicon substrates by Langmuir-Blodgett technique as closely spaced monolayers of 20-40 μm size. Hydrazine exposure followed by annealing in vacuum and argon ambient results in the formation of reduced graphene oxide (RGO) monolayers, without significantly affecting the overall morphology of the sheets. The monolayer character of both GO and RGO sheets was ascertained by atomic force microscopy. X-ray photoelectron spectroscopy supported by Fourier transform infrared spectroscopy revealed that the reduction process results in a significant decrease in oxygen functionalities, accompanied by a substantial decrease in the ratio of non-graphitic to graphitic (sp² bonded) carbon in the monolayers from 1.2 to 0.35. Raman spectra of GO and RGO monolayers have shown that during the reduction process, the G-band shifts by 8-12 cm^− 1 and the ratio of the intensities of D-band to G-band, I(D)/I(G) decreases from 1.3 ± 0.3 to 0.8 ± 0.2, which is in tune with the smaller non-graphitic carbon content of RGO monolayers. The significant decrease in I(D)/I(G) has been explained by assuming that substantial order is present in precursor GO monolayers as well as RGO monolayers obtained by solid state reduction.     

Origin of visible photoluminescence from porous silicon as studied by Raman spectroscopy

In this paper we discuss the different models proposed to explain the visible luminescence in porous silicon (PS). We review our recent photoluminescence and Raman studies on PS as a function of different preparation conditions and isochronal thermal annealing. Our results can be explained by a hybrid model which incorporates both nanostructures for quantum confinement and silicon complexes (such as SiH _x and siloxene) and defects at Si/SiO₂ interfaces as luminescent centres.     

Small-sized carbon nanohorns enabling cellular uptake control

Carbon nanotubes perform well in preclinical tests for drug delivery and diagnostic imaging, but controlling the size at less than 100 nm to avoid nonspecific uptake by reticuloendothelial systems while targeting delivery to cells of interest via receptor-mediated endocytosis is difficult, which currently limits their widespread use. Herein, 20-50-nm graphene tubules, small-sized single-walled carbon nanohorns (S-SWNHs), are obtained with a yield of 20% or higher by an oxidative exfoliation of 100 nm pristine SWNH aggregates. S-SWNHs are highly hydrophilic and remarkably resistant to cellular uptake by macrophages (RAW 264.7 cells), tumor cells (HeLa or KB), or normal cells (FHs 173We). The nonstimulatory property to cell membranes therefore makes cellular uptake control of S-SWNHs by functionalization easy. By attaching phospholipid polyethylene glycol, the cellular internalization of S-SWNHs is almost completely inhibited in RAW 264.7 macrophages. When functionalized with tumor-targeting folic acid (FA), FA-S-SWNHs are taken up by FA receptor-overexpressing KB cells but not by normal human embryonic cells (FHs 173We), which do not express the FA receptor. With a high rate of stealth and targeting in vitro, S-SWNHs are one of the most promising nanoparticles for medical use.     

Diagnosis of breast cancer by analysis of sialic acid concentrations in human saliva by surface-enhanced Raman spectroscopy of silver nanoparticles

Breast cancer is the most common type of malignant tumor among women and their second leading cause of cancer-related deaths.The most common method for screening and diagnosis is mammography.Nonetheless,two main problems have been identified.First,the dose of radiation received during the test prevents the method from the use on women who are ＜ 40 years old.Second,there can be mammogram failure owing to the lack of tumor contrast with the fibrous tissue.Therefore,there is a need for screening methods that will help to identify high-risk cases.We developed a biological marker test that can help to identify them.Increased levels of sialic acid (SA) in saliva are known to correlated with breast cancer.In this study,we evaluated the feasibility of Raman spectroscopy as a method for quantification of SA in saliva,using citrate-reduced silver nanoparticles (cit-Ag-NPs) as a surface-enhanced Raman spectroscopy (SERS) substrate.Quantification of SA was accomplished by measuring its intensity in saliva and comparing it with a calibration curve of SA standards.The mean SA concentration in saliva was found to be significantly higher among 100 breast cancer patients (18.3 ± 9.4 mg·dL-1;mean ± SD) than among 106 healthy controls (3.5 ± 1.0 mg·dL-1).The SERS test showed sensitivity of 94％ and specificity 98％ for detection of patients with breast cancer,assuming that SA concentration ＞ 7 mg·dL-1 is a cutoff for positive test results.Our findings prove the usefulness of this SERS technique as a simple,convenient,and highly sensitive method of quantitative analysis of SA in saliva.The simplicity of this nanotechnological test may help to substantially reduce the mortality among patients with breast cancer by providing women with a simple,noninvasive screening test that can be applied regardless of age or density of breast tissue.     

Raman spectroscopy and imaging of graphene

Graphene has many unique properties that make it an ideal material for fundamental studies as well as for potential applications. Here we review recent results on the Raman spectroscopy and imaging of graphene. We show that Raman spectroscopy and imaging can be used as a quick and unambiguous method to determine the number of graphene layers. The strong Raman signal of single layer graphene compared to graphite is explained by an interference enhancement model. We have also studied the effect of substrates, the top layer deposition, the annealing process, as well as folding (stacking order) on the physical and electronic properties of graphene. Finally, Raman spectroscopy of epitaxial graphene grown on a SiC substrate is presented and strong compressive strain on epitaxial graphene is observed. The results presented here are highly relevant to the application of graphene in nano-electronic devices and help in developing a better understanding of the physical and electronic properties of graphene. This article is published with open access at Springerlink.com     

Carbon nanotube-tipped endoscope for in situ intracellular surface-enhanced Raman spectroscopy

Gold nanoparticle-decorated carbon nanotubes (CNTs) are used to study intracellular environments in situ using surface-enhanced Raman spectroscopy (SERS). CNTs are decorated with gold nanoparticles and assembled onto the tips of pulled glass capillaries to form a SERS-enabled endoscope. The sub-micrometer size and high mechanical strength of the endoscope make it possible to penetrate the cell membrane for intracellular probing and remain positioned inside during lengthy SERS measurements without causing damage to the cell. Using the SERS-enabled endoscope, DNA and other biomolecules are detected in situ within the nucleus of a single human cervical carcinoma cell in a minimally invasive manner. The SERS-enabled endoscopes exhibit high selectivity and sensitivity for detecting trace amounts of analytes (≈1 pM) in biofluid environments, highlighting their capabilities as label-free, biological sensors for real-time in situ cellular diagnostics, biological detection, and pharmaceutical research.     

The interplay of monolayer structure and serum protein interactions on the cellular uptake of gold nanoparticles

A critical factor for controlling serum albumin binding is surface hydrophobicity, which in turn decreases the cellular uptake of gold nanoparticles. Hydrophobic nanoparticles bind albumin more tightly, inhibiting particle uptake, with a direct correlation observed between uptake and surface hydrophobicity.     

One‐Pot Synthesis of Multifunctional Au@Graphene Oxide Nanocolloid Core@Shell Nanoparticles for Raman Bioimaging,Photothermal, and Photodynamic Therapy

The paper reports a facile one‐pot synthesis of core@shell nanoparticles (NPs) composed of Au core and graphene oxide nanocolloid (GON) shell. Unique properties of Au NPs and GON can be incorporated into a single nanohybrid structure to provide desirable functions for theranosis such as localized surface plasmon resonance, Raman scattering, amphiphilic surface, and photothermal conversion. Synthesis of Au@GON NPs is achieved by simple one‐pot reaction in aqueous phase utilizing GON as a reducing and stabilizing agent without any additional reducing agent. The zinc phthalocyanine, a photosensitizer, loaded Au@GON NPs show excellent multifunctional properties for combinational treatment of photothermal and photodynamic therapy in addition to Raman bioimaging with low cytotoxicity.     

Stable and unique graphitic Raman internal standard nanocapsules for surface-enhanced Raman spectroscopy quantitative analysis

Graphitic nanomaterials have unique, strong, and stable Raman vibrations that have been widely applied in chemistry and biomedicine. However, utilizing them as internal standards (ISs) to improve the accuracy of surface-enhanced Raman spectroscopy (SERS) analysis has not been attempted. Herein, we report the design of a unique IS nanostructure consisting of a large number of gold nanoparticles (AuNPs) decorated on multilayered graphitic magnetic nanocapsules (AGNs) to quantify the analyte and eliminate the problems associated with traditional ISs. The AGNs demonstrated a unique Raman band from the graphitic component, which was localized in the Raman silent region of the biomolecules, making them an ideal IS for quantitative Raman analysis without any background interference. The IS signal from the AGNs also indicated superior stability, even under harsh conditions. With the enhancement of the decorated AuNPs, the AGN nanostructures greatly improved the quantitative accuracy of SERS, in particular the exclusion of quantitative errors resulting from collection loss and non-uniform distribution of the analytes. The AGNs were further utilized for cell staining and Raman imaging, and they showed great promise for applications in biomedicine.

Open image in new window

     

Silver nanoparticles deposited on anodic aluminum oxide template using magnetron sputtering for surface-enhanced Raman scattering substrate

Low-cost and highly sensitive surface-enhanced Raman scattering (SERS) substrates have been fabricated by a simple anodizing process and a magnetron sputtering deposition. The substrates, which consist of silver nanoparticles embedded on anodic aluminum oxide (AAO) templates, are investigated by a scanning electron microscope and a confocal Raman spectroscopy. The SERS activities are demonstrated by Raman scattering from adsorbed solutions of methylene blue and pyridine on the SERS substrate surface. The most optimized SERS substrate contains the silver nanoparticles, with a size distribution of 10-30 nm, deposited on the AAO template. From a calculation, the SERS enhancement factor is as high as 8.5 × 10⁷, which suggests strong potentials for direct applications in the chemical detection and analyses.     

以氧化石墨烯为氧化介质制备石墨烯/聚苯胺导电复合材料

采用超声辅助Hummers法制得厚度约为1 nm的氧化石墨烯, 以其为氧化介质与苯胺反应合成了石墨烯/聚苯胺(RGO/PANI)导电复合材料。利用AFM、SEM、XRD和FTIR对反应所得产物进行了表征。结果表明: 苯胺在略高于室温的酸性水溶液中可以对氧化石墨烯(GO)进行还原, 而苯胺自身则被氧化石墨烯中大量的含氧基团氧化并发生聚合反应, 最终生成RGO/PANI导电复合材料, 当苯胺用量为1 mL, 氧化石墨烯用量为0.1 g, 在水浴温度为70 ℃下剧烈搅拌24 h时, 获得的RGO/PANI复合材料导电性最佳, 约为10 S/cm。     

Functionalizing metal nanostructured film with graphene oxide for ultrasensitive detection of aromatic molecules by surface-enhanced Raman spectroscopy

Surface-enhanced Raman spectroscopy (SERS) as a powerful analytical tool has gained extensive attention. Despite of many efforts in the design of SERS substrates, it remains a grand challenge for creating a general substrate that can detect diverse target analytes. Herein, we report our attempt to address this issue by constructing a novel metal-graphene oxide nanostructured film as SERS substrate. Taking advantages of the high affinity of graphene oxide (GO) toward aromatic molecules and the SERS property of nanostructured metal, this structure exhibits great potential for diverse aromatic molecules sensing, which is demonstrated by using crystal violet (CV) with positive charge, amaranth with negative charge, and neutral phosphorus triphenyl (PPh(3)) as model molecules.     

Ultraviolet-visible and surface-enhanced Raman scattering spectroscopy studies on self-assembled films of ruthenium phthalocyanine on organic monolayer-modified silver substrates

A self-assembled film of ruthenium phthalocyanine (RuPc) fabricated on a silver substrate pre-modified with a monolayer of 4-mercaptopyridine (PySH) or 1,4-bis[2-(4-pyridyl)ethenyl]-benzene (BPENB) was studied by ultraviolet-visible (UV-Vis) and surface enhanced Raman scattering (SERS) spectroscopy. PySH or BPENB was used as a ligand to link RuPc since they not only modify the silver substrate, but also deliver a pyridyl group pointing out from the silver surface. Therefore, we can explore the relationship between the structure and orientation of metallophthalocyanine and the substrate modified by the two kinds of organic-monolayers with the different conjugates and molecular lengths. UV-Vis bands due to the organic-monolayer (PySH or BPENB) modified silver films shift to longer wavelengths and a new band arising from the metallophthlocyanine appears, suggesting the binding of RuPc to PySH/BPENB, as well as the interaction between the marcocycle of RuPc and the ring of PySH/BPENB. Vibrational bands arising from both the RuPc and PySH/BPENB moieties appear clearly in the SERS spectra of the RuPc-PySH/BPENB composite films, indicating that RuPc is successfully assembled on the top of PySH/BPENB film. The shifts and relative intensity changes of bands due to PySH or BPENB in the SERS spectra imply the binding of the metallophthalocyanine to the pyridyl group in the composite films. Furthermore, the comparison of the SERS spectra revealed that the orientations of PySH and BPENB in the two kinds of composite films are different; the BPENB moiety in the RuPc-BPENB composite film is more perpendicular to the silver surface compared with the PySH moiety in the RuPc-PySH composite film.     

Direct measurement of the Raman enhancement factor of rhodamine 6G on graphene under resonant excitation

Graphene substrates have recently been found to generate Raman enhancement. Systematic studies using different Raman probes have been implemented, but one of the most commonly used Raman probes, rhodamine 6G （R6G）, has yielded controversial results for the enhancement effect on graphene. Indeed, the Raman enhancement factor of R6G induced by graphene has never been measured directly under resonant excitation because of the presence of intense fluorescence backgrounds. In this study, a polarization-difference technique is used to suppress the fluorescence background by subtracting two spectra collected using different excitation laser polarizations. As a result, enhancement factors are obtained ranging between 1.7 and 5.6 for the four Raman modes of R6G at 611, 1,183, 1,361, and 1,647 cm-~ under resonant excitation by a 514.5 nm laser. By comparing these results with the results obtained under non-resonant excitation （632.8 nm） and pre-resonant excitation （593 nm）, the enhancement can be attributed to static chemical enhancement （CHEM） and tuning of the molecular resonance. Density functional theory simulations reveal that the orbital energies and densities for R6G are modified bv ~raphene dots.     

Mesoflowers: A new class of highly efficient surface-enhanced Raman active and infrared-absorbing materials

A method for the synthesis of a new class of anisotropic mesostructured gold material, which we call “mesoflowers”, is demonstrated. The mesoflowers, unsymmetrical at the single particle level, resemble several natural objects and are made up of a large number of stems with unusual pentagonal symmetry. The mesostructured material has a high degree of structural purity with star-shaped, nano-structured stems. The mesoflowers were obtained in high yield, without any contaminating structures and their size could be tuned from nano- to meso-dimensions. The dependence of various properties of the mesoflowers on their conditions of formation was studied. The near-infrared-infrared (NIR-IR) absorption exhibited by the mesoflowers has been used for the development of infrared filters. Using a prototypical device, we demonstrated the utility of the gold mesoflowers in reducing the temperature rise in an enclosure exposed to daylight in peak summer. These structures showed a high degree of surface-enhanced Raman scattering (SERS) activity compared to spherical analogues. SERS-based imaging of a single mesoflower is demonstrated. The high SERS activity and NIR-IR absorption property open up a number of exciting applications in diverse areas. Electronic Supplementary Material  Supplementary material is available in the online version of this article at http://dx.doi.org/ and is accessible free of charge.     

Gold nanoparticles/graphene oxide composite for electrochemical sensing of hydroxylamine and hydrogen peroxide

It has been discovered that the complex formed by cetyltrimethyl ammonium bromide (CTAB) and graphene oxide (GO) is highly stable in aqueous solution and adhesive to the glassy carbon electrode (GCE) surface in our previous research. In this work, the film of CTAB/GO complex was directly formed on GCE and gold nanoparticles were facilely incorporated into the matrix of CTAB/GO complex at the same time. Scanning electron microscopic (SEM) investigation shows that gold nanoparticles were distributed uniformly on the sheets of graphene. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and amperometry were used to investigate the electrochemical behaviors of AuNP/CTAB/GO. The obtained AuNP/CTAB/GO presents excellent catalytic capabilities towards the oxidation of hydroxylamine (HA) and the reduction of H₂O₂. The oxidation current of HA and the reduction current of H₂O₂ are linear with their concentrations in the range of 10～1000 μM and 1.0～5000 μM, respectively. The detection limits for HA and H₂O₂ are 3.5 μM and 0.67 μM, respectively. The mechanism of the oxidation of HA on AuNP/CTAB/GO modified GCE was also studied.     

氧化石墨烯的制备及结构研究进展

氧化石墨烯是一种表面含有丰富的含氧官能团石墨烯衍生物.氧化石墨烯拥有较大的比表面积、良好的亲水性和生物亲和性,被广泛应用于传感器、储能材料、药物载体、催化等领域.本文介绍了近几年氧化石墨烯的制备方法,简述了由Hummers法制备氧化石墨烯的生成机理,主要概括了氧化石墨烯新的结构模型,提出寻找高效绿色的氧化剂是制备氧化石墨烯的关键,确定氧化石墨烯的结构对其表面改性及在复合材料的应用和发展有重要的影响.