Since 2000, there has been an explosion of activity in the field of plasmon-enhanced Raman spectroscopy (PERS), including surface-enhanced Raman spectroscopy (SERS), tip-enhanced Raman spectroscopy (TERS) and shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). In this Review, we explore the mechanism of PERS and discuss PERS hotspots — nanoscale regions with a strongly enhanced local electromagnetic field — that allow trace-molecule detection, biomolecule analysis and surface characterization of various materials. In particular, we discuss a new generation of hotspots that are generated from hybrid structures combining PERS-active nanostructures and probe materials, which feature a strong local electromagnetic field on the surface of the probe material. Enhancement of surface Raman signals up to five orders of magnitude can be obtained from materials that are weakly SERS active or SERS inactive. We provide a detailed overview of future research directions in the field of PERS, focusing on new PERS-active nanomaterials and nanostructures and the broad application prospect for materials science and technology. Assisted by rationally designed novel plasmonic nanostructures, surface-enhanced Raman spectroscopy has presented a new generation of analytical tools (that is, tip-enhanced Raman spectroscopy and shell-isolated nanoparticle-enhanced Raman spectroscopy) with an extremely high surface sensitivity, spatial resolution and broad application for materials science and technology.

Nanostructure-based plasmon-enhanced Raman spectroscopy for surface analysis of materials

The well-defined silver (Ag) nanowires with five-twinned structure have been prepared by polyol reduction in the presence of poly(vinylpyrrolidone) (PVP K-30, 40 000). The obtained Ag nanowires are nearly monodispersed with an average diameter of 70 nm and length of 6 μm. It is confirmed from the results of thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and Fourier transform Raman spectra (FT-Raman) that one monolayer of the PVP molecules might be absorbed on the surface of the Ag nanowires through Ag−O coordination. On the basis of the experimental analysis, the probable spatial conformation of the PVP molecules is supposed to be that the CH skeleton chain of the PVP is close to the surface of the Ag nanowires. The pyrrolidone ring might be tilted on the surface of the Ag nanowires through Ag:O coordination. These results may provide direct evidence for the role of the PVP molecules in the formation of the Ag nanowires.

Evidence for the Monolayer Assembly of Poly(vinylpyrrolidone) on the Surfaces of Silver Nanowires

Covalent attachment of a non-fluorinated polyetherimide onto the surface of carboxylic acid-functionalized multiwalled carbon nanotubes (MWNTs) has been achieved via grafting reactions. This confirms for the first time that the grafting reaction occurs at the nanotube surface when the carboxylic acid-functionalized MWNTs react with the polyetherimide with amine-terminated groups, through both amide and imide linkages formed at the interface between the carbon nanotubes and the polyetherimide. Additionally, an increase in the average molecular weight is detected in gel permeation chromatography when the polyetherimide is chemically attached onto the nanotubes. More interestingly, the chemical bonding at the interface provides much better interfacial adhesion and mechanical stress transfer, evidenced by a significant improvement in mechanical properties. As a result of the chemical attachment, the carbon nanotube-reinforced polyetherimide composite films have enhanced electrical conductivity, thermal deform...

Multiwalled Carbon Nanotubes with Chemically Grafted Polyetherimides

Polyimide nanocomposites with boron nitride-coated multi-walled carbon nanotubes (BN-c-MWCNTs) were successfully prepared with enhanced thermal conductivity and electrical insulation The inorganic BN nano-layer on the MWCNT surface provides electrical insulation and prevents the formation of MWCNT electrically conductive networks in the PI matrix BN-c-MWCNT/PI films exhibited synchronously good thermal conductivity and relatively high electrical resistivity Compared with that of pure PI, the thermal conductivity of the BN-c-MWCNT/PI films with 3 wt% BN-c-MWCNTs increased by 106% In addition, the electrical insulation of the BN-c-MWCNT/PI films was also improved compared with that of the MWCNT/PI composite films All the above-mentioned properties provide advantages to the PI hybrid films in electronic packaging and electrical insulation

Polyimide nanocomposites with boron nitride-coated multi-walled carbon nanotubes for enhanced thermal conductivity and electrical insulation

Currently, a lot of research efforts have been directed toward exploiting the special high-performance characteristics of polymers with sulfur in the backbone. Sulfur-containing polymers fall under various classes and cover an extremely broad property range. The impetus to their development resulted from the unique properties and success in their applications, depending upon the type of linkage introduced. This review basically sets out to explain the design, synthesis, properties, and applications of various sulfur-containing polymers especially polyamides, polyimides, poly(amide-imide)s, polybenzimidazoles, polyurethanes, polyesters, etc. Outstanding performance of these polymers came up from their structures having sulfur-based groups such as thiophene, sulfide, sulfone, thiazol, and thiourea. Thus these linkages endow special features to such functional polymers. The sulfur-containing polymers are also described here with reference to their relevance as optically active, liquid crystalline, flame reta...

Recent Developments in Sulfur-Containing Polymers

Surface lamellar decoration (SLD), surface enhanced Raman scattering (SERS) and optical second harmonic generation (SHG) experiments have been utilized to study the molecular orientation and conformation changes at a rubbed polyimide alignment-layer surface. This aromatic polyimide containing pendent cyanobiphenyl mesogens was synthesized via a polycondensation of 2,2'-bis(3,4-dicarboxy-phenyl)hexafluoropropane dianhydride (6FDA) with bis[omega-[4-(4-cyanophenyl)phenoxy]hexyl] 4,4'-diamino-2,2'-biphenyldicarboxylate (nCBBP, n = 6), abbreviated as 6FDA--6CBBP. Uniform alignment layers, possessing high pretilt angles ranging from 39 degrees to 43 degrees, have been achieved after mechanical rubbing of the polyimide thin film surface at room temperature and subsequent annealing. This is the first time that high pretilt angles have been detected to possess a negative angle (-theta(c)) with respect to the rubbing direction (i.e., opposite to the rubbing direction), considerably different from the conventional pretilt angle (theta(c)) observed along the rubbing direction. This observation is confirmed using magnetic null and SHG methods. Combined polyethylene (PE) SLD and atomic force microscopy experiments reveal that the azimuthal orientation distribution of the long axis of the edge-on PE lamellar crystals is oriented normal to the rubbing direction, indicating that the PE chains are aligned parallel to the rubbing direction. This SLD technique probes the anisotropic surface orientation of the outermost molecules of the rubbed polyimide layer. The SERS results show that prior to rubbing the surface, both the pendent cyanobiphenyls in the side chains and backbones possess nearly planar chain conformations at the polyimide surface. Mechanical rubbing causes not only tilting of the backbone moieties, such as imide-phenylene structure, but also significant conformational rearrangements of the pendent side chains at the surfaces. The molecular mechanism of this unusual alignment is due to the fact that the pendent cyanobiphenyls forms a uniformly tilted conformation on the rubbed surface, and the polar cyano groups point down toward the layer surface deduced from SHG phase measurements. This conformational rearrangement of the side chains results in the formation of fold-like bent structures on the surface, which directly leads to the long axis of cyanobiphenyls having the -theta(c) pretilt angle with respect to the rubbing direction.

Rubbing-induced molecular reorientation on an alignment surface of an aromatic polyimide containing cyanobiphenyl side chains.

Two polyimides having the same backbone chemical structure and different pendant side groups at the 2- and 2′-positions of the diamine, the six methylene units capped with 4-cyanobiphenyl end groups and trifluoromethyl, were synthesized (6FDA-6CBO and 6FDA-PFMB). Surface-enhanced Raman scattering and surface optical second harmonic generation measurements show that after rubbing the major change in 6FDA-PFMB surface appears in the orientation of the dianhydride, which was originally planar, but becomes tilted with respect to the surface plane. In the case of 6FDA-6CBO, rubbing also causes the originally planar 4-cyanobiphenyls to tilt away from the surface and assume an azimuthally anisotropic distribution.

Surface studies of polyimide thin films via surface-enhanced Raman scattering and second harmonic generation

Two-arm poly(ethylene oxide) fractions (PEOs) with arm lengths of 2 220 g/mol were synthesized via a reaction using terephthaloyl (1,4-), isophthaloyl (1,3-) and phthaloyl (1,2-) dichorides as coupling agents The center of each molecule thus includes a phenylene group as a configurational defect, and they are excluded to the crystal folded basal surfaces In the lamellar crystals with the once-folded overall molecular conformation, observations of surface-enhanced Raman scattering experiments show that only the in-plane vibration modes are selectively enhanced This implies that the arrangement of phenylene groups adopts a “stand-up” orientation on the basal surface, i e, the π plane of phenylene groups in the defects is perpendicular to the lamellar basal surface

Gi Xue

Papers

Rubbing-induced molecular reorientation on an alignment surface of an aromatic polyimide containing cyanobiphenyl side chains.

Surface studies of polyimide thin films via surface-enhanced Raman scattering and second harmonic generation

Defect orientation on the chain folded surfaces of two-arm poly(ethylene oxide) lamellar crystals

Chemically deposited silver film used as a sers-active over-coating layer for polymer film *