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The structure and polymer–nanoparticle interactions among physically adsorbed poly(2-vinylpyridine) chains on the surface of silica nanoparticles (NPs) were systematically studied as a function of molecular weight (MW) by sum frequency generation (SFG) and X-ray photoelectron (XPS) spectroscopies. Analysis of XPS data identified hydrogen bonds between the polymer and NPs, while SFG evaluated the change in the number of free OH sites on the NP’s surface. Our data revealed that the hydrogen bonds and amount of the free −OH sites have a significant dependence on the polymer’s MW. These results provide clear experimental evidence that the interaction of physically adsorbed chains with nanoparticles is strongly MW dependent and aids in unraveling the microscopic mechanism responsible for the strong MW dependence of dynamics of the interfacial layer in polymer nanocomposites.

The free radical and controlled radical polymerization of sodium 4-vinylbenzenesulfonate using graphene oxide as a radical initiator was studied. This work demonstrates that graphene oxide can initiate radical polymerization in an aqueous solution without any additional initiator. Poly(sodium 4-vinylbenzenesulfonate) obtained via reversible addition–fragmentation chain transfer polymerization had a controlled molecular weight with a very narrow polydispersity ranging between 1.01 and 1.03. The reduction process of graphene oxide as well as the resulting composite material properties were analyzed in detail.

International audience; Polymerized ionic liquids (PolyILs) are promising candidates for a broad range of technologies. However, the relatively low conductivity of PolyILs at room temperature has strongly limited their applications. In this work, we provide new insights into the roles of various microscopic parameters controlling ion transport in these polymers, which are crucial for their rational design and practical applications. Using broadband dielectric spectroscopy and neutron and light scattering techniques, we found a clear connection between the activation energy for conductivity, fast dynamics, and high-frequency shear modulus in PolyILs at their glass transition temperature (Tg). In particular, our analysis reveals a correlation between conductivity and the amplitude of fast picosecond fluctuations at Tg, suggesting the possible involvement of fast dynamics in lowering the energy barrier for ion conductivity. We also demonstrate that both the activation energy for ion transport and the amplitude of the fast fluctuations depend on the high-frequency shear moduli of PolyILs, thus identifying a practically important parameter for tuning conductivity. The parameters recognized in this work and their connection to the ionic conductivity of PolyILs set the stage for a deeper understanding of the mechanism of ion transport in PolyILs in the glassy state.

International audience; The addition of hard fillers to a polymer matrix is a well-known process for achieving mechanical reinforcement. With a decrease in the size of the fillers, the contribution from polymer–particle nanometer-sized interfaces becomes significant, and these interfaces affect the mechanical performance of polymer nanocomposites (PNCs) beyond the limits established for conventional composites. However, the molecular mechanisms underlying the improvement in the mechanical performance of glassy PNCs remain unresolved, necessitating a deeper understanding of the structure–property relationships in these intrinsically heterogeneous systems. In this effort, by using Brillouin light scattering (BLS) and dynamic mechanical analysis (DMA), we demonstrated that adding shorter chains to a PNC prepared with high molecular weight polymers significantly improved the mechanical properties of the PNC in the glassy state. The strongest enhancement of mechanical properties occurred at an optimum concentration of short chains. This is in contrast to the behavior of the glass transition temperature of PNCs which shows a monotonic decrease with an increase in the concentration of shorter chains. Using experimental data and coarse-grained molecular dynamics (MD) simulations, we have identified the molecular mechanism leading to the observed nonmonotonic changes in mechanical reinforcement. This mechanism includes changes in the nanoscale organization at the interface combined with chain stretching amplified by the addition of the short chains. Overall, our approach paves a simple and cost-effective pathway to fabricating glassy PNCs with significantly improved mechanical properties that will fill various practical needs.

We analyze conductivity of polymerized ionic liquids with focus on fundamental limitations hindering faster charge transport in polymer electrolytes. We emphasize that to achieve the required ionic conductivity ∼10−3 S/cm in dry polymer electrolytes, a decoupling of ion transport from segmental dynamics is required. We demonstrate that two competing mechanisms control decoupling of ion transport: electrostatic interactions that dominates for small ions such Li, and elastic force that dominates for large ions. Our experimental results indeed confirm significant contribution of the elastic force to the energy barrier controlling transport of large ions. We also emphasize importance of ion-ion correlations that strongly affect charge transport (conductivity) even at the same ion diffusivity. Our analysis suggests that these correlations suppress ion conductivity in polymer electrolytes by about ten times. At the end, we formulate some ideas on design of polymer electrolytes with high ion conductivity.

Despite the wide use of polymer nanocomposites (PNCs) in various applications, our understanding of the microscopic parameters controlling their macroscopic properties remains limited. In this study, we examine the dielectric strength of segmental dynamics, ΔeIL(T) in the interfacial polymer layer surrounding the nanoparticles in PNCs. The presented analysis reveals a significant drop in ΔeIL(T) and its anomalous temperature dependence in the polymer layer adsorbed to nanoparticles. The drop in ΔeIL(T) was observed in all samples regardless of whether segmental relaxation time in the interfacial layer was slower or faster than in the bulk polymer, excluding interpretation of the “dead” layer. We ascribe the observed decrease in the dielectric strength to the restricted amplitude of segmental relaxation in the interfacial/adsorbed layer. Our results provide a new perspective on discussion of dynamics in the interfacial layer in PNCs and thin polymer films, demonstrating that not only segmental relaxation time but also its amplitude can be strongly affected by the interface.

The self-diffusion of a single large particle in a fluid is usually described by the classic Stokes–Einstein (SE) hydrodynamic relation. However, there are many fluids where the SE prediction for nanoparticles diffusion fails. These systems include diffusion of nanoparticles in porous media, in entangled and unentangled polymer melts and solutions, and protein diffusion in biological environments. A fundamental understanding of the microscopic parameters that govern nanoparticle diffusion is relevant to a wide range of applications. In this work, we present experimental measurements of the tracer diffusion coefficient of small and large nanoparticles that experience strong attractions with unentangled and entangled polymer melt matrices. For the small nanoparticle system, a crossover from suppressed to enhanced diffusion is observed with increasing polymer molecular weight. We interpret these observations based on our theoretical and simulation insights of the preceding article (paper 1) as a result of a ...

While PLA possesses modest to good strength and stiffness, broader application is hindered by its brittle nature. The aim of this study was to develop strong and tough polymeric materials from renewable biomaterials and understand the underlying interactions and mechanisms. Cellulose nanofibrils (CNFs) and epoxidized soybean oil (ESO) were compounded with poly(lactic acid) (PLA) to create a PLA-CNF-ESO tertiary nanocomposite system. Tensile and dynamic mechanical analyses were performed to see how variations in ESO and CNF content affect mechanical properties such as strength, modulus, ductility, and toughness. It was found that at low CNF levels (10 wt%) the addition of ESO can improve the ductility of the nanocomposites 5- to 10-fold with only slight losses in strength and modulus, while at higher CNF levels (20 and 30 wt%), ESO exhibited little effect on mechanical properties, possibly due to percolation of CNFs in the matrix, dominating stress transfer. Therefore, it is important to optimize CNF and ESO amounts in composites to achieve materials with both high strength and high toughness. Efforts have been made to understand the underlying mechanisms of the mechanical behavior of one class of these composites via thermal, dynamic mechanical, rheological, morphological, and Raman analyses.

Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. This phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing the same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated ...

Polymer membranes with the capability to process a massive volume of gas are especially attractive for practical applications of gas separation. Although much effort has been devoted to develop novel polymer membranes with increased selectivity, the overall gas-separation performance and lifetime of membrane are still negatively affected by the weak mechanical performance, low plasticization resistance and poor physical aging tolerance. Recently, elastic polymer membranes with tunable mechanical properties have been attracting significant attentions due to their tremendous potential applications. Herein, we report a series of urethane-rich PDMS-based polymer networks (U-PDMS-NW) with improved mechanical performance for gas separation. The cross-link density of U-PDMS-NWs is tailored by varying the molecular weight (Mn) of PDMS. The U-PDMS-NWs show up to 400% elongation and tunable Young’s modulus (1.3–122.2 MPa), ultimate tensile strength (1.1–14.3 MPa), and toughness (0.7–24.9 MJ/m3). All of the U-PDMS-N...

Tip-enhanced Raman spectroscopy (TERS) has been established as one the most efficient analytical techniques for probing vibrational states with nanoscale resolution. While TERS may be a source of unique information about chemical structure and interactions, it has a limited use for materials with rough or sticky surfaces. Development of the TERS approach utilizing a non-contact scanning probe microscopy mode can significantly extend the number of applications. Here we demonstrate a proof of the concept and feasibility of a non-contact TERS approach and test it on various materials. Our experiments show that non-contact TERS can provide 10 nm spatial resolution and a Raman signal enhancement factor of 105, making it very promising for chemical imaging of materials with high aspect ratio surface patterns and biomaterials.

It is generally believed that the strength of the polymer-nanoparticle interaction controls the modification of near-interface segmental mobility in polymer nanocomposites (PNCs). However, little is known about the effect of covalent bonding on the segmental dynamics and glass transition of matrix-free polymer-grafted nanoparticles (PGNs), especially when compared to PNCs. In this article, we directly compare the static and dynamic properties of poly(2-vinylpyridine)/silica-based nanocomposites with polymer chains either physically adsorbed (PNCs) or covalently bonded (PGNs) to identical silica nanoparticles (RNP = 12.5 nm) for three different molecular weight (MW) systems. Interestingly, when the MW of the matrix is as low as 6 kg/mol (RNP/Rg = 5.4) or as high as 140 kg/mol (RNP/Rg= 1.13), both small-angle X-ray scattering and broadband dielectric spectroscopy show similar static and dynamic properties for PNCs and PGNs. However, for the intermediate MW of 18 kg/mol (RNP/Rg = 3.16), the difference between physical adsorption and covalent bonding can be clearly identified in the static and dynamic properties of the interfacial layer. We ascribe the differences in the interfacial properties of PNCs and PGNs to changes in chain stretching, as quantified by self-consistent field theory calculations. These results demonstrate that the dynamic suppression at the interface is affected by the chain stretching; that is, it depends on the anisotropy of the segmental conformations, more so than the strength of the interaction, which suggests that the interfacial dynamics can be effectively tuned by the degree of stretching-a parameter accessible from the MW or grafting density.

We report the observation of oscillatory redox reactions on the surface of multilayer graphene oxide (GO) films at room temperature. The redox reactions exhibited dampened oscillatory behavior with a period of about 5 days and were found to be dependent on the time elapsed from film deposition. The kinetic behavior observed for the oxidation–reduction reactions and the metastability of the surface functional groups are adequately described by two models involving GO reactions and reactant diffusion.

Additive Manufacturing (AM) of metals is a potentially disruptive technology that could significantly change the industrial supply chain. There are a limited number of AM methods capable of creating metal parts, and one method showing significant potential is Binder Jet AM (Binder Jetting). Binder Jetting utilizes an inkjet print head to deposit a binder fluid onto a powder bed and bind together powder particles into a desired geometry. This study investigates a new binder system consisting of a difunctional monomer, triethylene glycol dimethacrylate (TEG-DMA). TEG-DMA exhibits excellent printability with an Ohnesorge’s number of .258 making the Z number 3.876. During the thermal curing process, the difunctional monomer polymerizes and crosslinks at the onset temperature of 138 °C, becoming a solid dimethacrylate network. When the binder is utilized within the stainless-steel powder bed at 200 °C, it forms a network incorporating the stainless-steel particles, binding the powder into any specified geometry. Crosslinking the monomer within the stainless-steel 420 powder bed imparts a flexural strength of 1.0–3.3 MPa to the green part depending on the volume of monomer in the part. After sintering, the final stainless-steel parts results in a void fraction close to 60 % and carbon content below 0.4 %.

Summary Separating rare-earth-element-rich minerals from unwanted gangue in mined ores relies on selective binding of collector molecules at the interface to facilitate froth flotation. Salicylhydroxamic acid (SHA) exhibits enhanced selectivity for bastnäsite over calcite in microflotation experiments. Through a multifaceted approach, leveraging density functional theory calculations, and advanced spectroscopic methods, we provide molecular-level mechanistic insight to this selectivity. The hydroxamic acid moiety introduces strong interactions at metal-atom surface sites and hinders subsurface-cation stabilization at vacancy-defect sites, in calcite especially. Resulting from hydrogen-bond-induced interactions, SHA lies flat on the bastnäsite surface and shows a tendency for multilayer formation at high coverages. In this conformation, SHA complexation with bastnäsite metal ions is stabilized, leading to advanced flotation performance. In contrast, SHA lies perpendicular to the calcite surface due to a difference in cationic spacing. We anticipate that these insights will motivate rational design and selection of future collector molecules for enhanced ore beneficiation., Graphical Abstract, Highlights • Salicylhydroxamic acid (SHA) is an effective collector for flotation of bastnäsite • DFT calculations show that the phenol group anchors SHA flat to bastnäsite surface • Spectroscopic results suggest SHA multilayers on bastnäsite at high coverage • This peculiar adsorption explains efficacy of SHA in bastnäsite flotation from ores, Chemical Engineering; Spectroscopy; Physical Inorganic Chemistry; Surface Chemistry

We report a novel approach to synthesize monodisperse hydrogel nanoparticles that are tunable in size. The distinctive feature of our approach is the use of a multicopper oxidase enzyme, laccase, as both a biocatalyst and template for nanoparticle growth. We utilize the ferroxidase activity of laccase to initiate localized production of iron(III) cations from the oxidation of iron(II) cations. We demonstrate that nanoparticles are formed in a dilute polymer solution of alginate as a result of cross-linking between alginate and enzymatically produced iron(III) cations. Exerting control over the enzymatic reaction allows for nanometer-scale tuning of the hydrogel nanoparticle radii in the range of 30–100 nm. The nanoparticles and their growth kinetics were characterized via dynamic light scattering, atomic force microscopy, and UV–vis spectroscopy. This finding opens up a new avenue for the synthesis of tunable nanoscale hydrogel particles for biomedical applications.

Polymerized ionic liquids (PolyILs) are promising candidates for a wide range of technological applications due to their single ion conductivity and good mechanical properties. Tuning the glass transition temperature (Tg) in these materials constitutes a major strategy to improve room temperature conductivity while controlling their mechanical properties. In this work, we show experimental and simulation results demonstrating that in these materials Tg does not follow a universal scaling behavior with the volume of the structural units Vm (including monomer and counterion). Instead, Tg is significantly influenced by the chain flexibility and polymer dielectric constant. We propose a simplified empirical model that includes the electrostatic interactions and chain flexibility to describe Tg in PolyILs. Our model enables design of new functional PolyILs with the desired Tg.

The modification of polymer dynamics in the presence of strongly interacting nanoparticles has been shown to significantly change the macroscopic properties above the glass transition temperature of polymer nanocomposites (PNCs). However, much less attention has been paid to changes in the dynamics of glassy PNCs. Analysis of neutron and light scattering data presented herein reveals a surprising enhancement of local dynamics, e.g., fast picosecond and secondary relaxations, in glassy PNCs accompanied with a strengthening of mechanical modulus. We ascribe this counter-intuitive behavior to the complex interplay between chain packing and stretching within the interfacial layer formed at the polymer-nanoparticle interface.

Nanolithography has become a driving force in advancements of the modern day's electronics, allowing for miniaturization of devices and a steady increase of the calculation, power, and storage densities. Among various nanofabrication approaches, scanning probe techniques, including atomic force microscopy (AFM), are versatile tools for creating nanoscale patterns utilizing a range of physical stimuli such as force, heat, or electric field confined to the nanoscale. In this study, the potential of using the electric field localized at the apex of an AFM tip to induce and control changes in the mechanical properties of an ion containing polymer—a polymerized ionic liquid (PolyIL)—on a very localized scale is explored. In particular, it is demonstrated that by means of AFM, one can form topographical features on the surface of PolyIL-based thin films with a significantly lower electric potential and power consumption as compared to nonconductive polymer materials. Furthermore, by tuning the applied voltage and ambient air humidity, control over dimensions of the formed structures is reproducibly achieved.

The need to produce large quantities of graphenic materials displaying excellent conductivity, thermal resistance, and tunable properties for industrial applications has spurred interest in new techniques for exfoliating graphite. In this paper, sonication-assisted exfoliation of graphitic precursors in the presence of chloroform is shown to produce chemically and structurally unique exfoliated graphitic materials in high yields. These exfoliated graphites, referred to as mesographite and mesographene, respectively, exhibit unique properties which depend on the number of layers and exfoliation conditions. Structural characterization of mesographene reveals the presence of nanoscale two-dimensional graphene layers, and three-dimensional carbon nanostructures sandwiched between layers, similar to those found in ball-milled and intercalated graphites. The conductivities of mesographite and mesographene are 2700 and 2000 S/m, respectively, indicating high conductivity despite flake damage. Optical absorption ...

A possible role of quantum effects, such as tunneling and zero-point energy, in the structural dynamics of supercooled liquids is studied by dielectric spectroscopy. Presented results demonstrate that the liquids, bulk 3-methylpentane 3MP and confined normal and deuterated water have low glass transition temperature and unusually low for their class of materials steepness of the temperature dependence of structural relaxation, or fragility. Although we do not find any signs of tunneling in structural relaxation of these liquids, their unusually low fragility can be well described by the influence of the quantum fluctuations. Confined water presents especially interesting case in comparison to the earlier data on bulk low-density amorphous and vapor deposited water. Confined water exhibits much weaker isotope effect than bulk water, although the effect is still significant. We show that it can be ascribed to the change of the energy barrier for relaxation due to a decrease in the zero-point energy upon D-H substitution. The observed difference in the behavior of confined and bulk water demonstrates high sensitivity of quantum effects to the barrier heights and structure of water. Moreover, these results demonstrate that extrapolation of confined water properties to the bulk water behavior is questionable., 24 pages, 6 figures

The mechanical reinforcement of polymer nanocomposites (PNCs) above the glass transition temperature, Tg, has been extensively studied. However, not much is known about the origin of this effect below Tg. In this Letter, we unravel the mechanism of PNC reinforcement within the glassy state by directly probing nanoscale mechanical properties with atomic force microscopy and macroscopic properties with Brillouin light scattering. Our results unambiguously show that the “glassy” Young’s modulus in the interfacial polymer layer of PNCs is two-times higher than in the bulk polymer, which results in significant reinforcement below Tg. We ascribe this phenomenon to a high stretching of the chains within the interfacial layer. Since the interfacial chain packing is essentially temperature independent, these findings provide a new insight into the mechanical reinforcement of PNCs also above Tg.

One century ago pioneering dielectric results obtained for water and n-alcohols triggered the advent of molecular rotation diffusion theory considered by Debye to describe the primary dielectric absorption in these liquids. Comparing dielectric, viscoelastic, and light scattering results we unambiguously demonstrate that the structural relaxation appears only as a high-frequency shoulder in the dielectric spectra of water. In contrast, the main dielectric peak is related to a supramolecular structure, analogous to the Debye-like peak observed in mono-alcohols., Comment: 5 pages, 3 figures

We performed Raman and Brillouin scattering measurements to estimate glass transition temperature, T(g), of hydrated protein. The measurements reveal very broad glass transition in hydrated lysozyme with approximate T(g) approximately 180+/-15 K. This result agrees with a broad range of T(g) approximately 160-200 K reported in literature for hydrated globular proteins and stresses the difference between behavior of hydrated biomolecules and simple glass-forming systems. Moreover, the main structural relaxation of the hydrated protein system that freezes at T(g) approximately 180 K remains unknown. We emphasize the difference between the "dynamic transition", known as a sharp rise in mean-squared atomic displacementr(2)at temperatures around T(D) approximately 200-230 K, and the glass transition. They have different physical origin and should not be confused.

Tip-enhanced Raman spectroscopy is considered a promising technique for imaging with nanoscale lateral resolution. However, its developments and use face many problems. In this paper we provide insight into the level of sample heating by the laser light in the presence of a metal-coated atomic force microscope (AFM) tip. The heating is attributed to the presence of an optical field enhanced by the tip. Sample temperatures were estimated using measurements of the ratio of the Stokes and anti-Stokes signals from a thin 50-nm sample on an Al substrate. A correlation between the heating and optical properties of the tips is established. The results demonstrate significant tip-induced heating (100 K and more) even at very low laser power. Copyright © 2009 John Wiley & Sons, Ltd.

An ultrathin aluminum oxide (Al2O3) coating improves significantly the stability of plasmonic structures used in tip enhanced Raman spectroscopy (TERS). The coating does not alter the favorable optical properties of metallic structures yet improves wear resistance and inhibits degradation, so that signal enhancement remains constant over 40 days for structures with a 3 nm thick protective coating. Most unprotected structures show substantial losses in enhancement over periods as short as 10 days when stored and used in ambient conditions.

The correlation between the fragility of glass-forming systems and the ratio of instantaneous bulk to shear moduli, K ∞/G ∞, of the corresponding glasses is analyzed for bulk metallic and polymeric materials. We emphasize the importance of the free electron contribution to the bulk modulus of metals and a specific intramolecular contribution to fragility in the case of polymers for some long molecules. We argue that these two contributions are the main reasons for the failure of the correlation between fragility and K ∞/G ∞ observed for these materials.

We have demonstrated that scanning nano-Raman spectroscopy (SNRS), generally known as tip-enhanced Raman spectroscopy (TERS), with side illumination optics can be effectively used for analysis of siliconbased structures at the nanoscale. Even though the side illumination optics has disadvantages such as difficulties in optical alignment and shadowing by the tip, it has the critical advantage that it may be used for the analysis of nontransparent samples. A key criterion for making SNRS effective for imaging Si samples is the optimization of the contrast between near-field and far-field (background) Raman signals. This has been achieved by optimizing the beam polarization, resulting in an order of magnitude improvement in the contrast. We estimate the lateral resolution of our Raman images to be ∼ 20 nm. Copyright  2007 John Wiley & Sons, Ltd.

Influence of pressure on fast dynamics and elastic properties in polyisobutylene is studied using Raman, Brillouin and neutron scattering spectroscopy. Analysis of the results shows that the boson peak frequency increases with pressure stronger than the longitudinal sound velocity measured by Brillouin scattering. Moreover, the boson peak intensity decreases under pressure stronger in Raman scattering than in neutron scattering suggesting a decrease in the light-to-vibrations coupling coefficient C ( ν ). The strong decrease of the microscopic peak intensity under pressure in Raman spectra supports this suggestion. We argue that variations in C ( ν ) might be related to amplitude of structural fluctuations. We speculate that change in disorder and/or overall density under pressure is the main cause for the observed variations.

The morphologies, electrical and mechanical properties and structure of polystyrene (PS) composites with varying concentrations of single-wall carbon nanotubes (SWNT) are analyzed. Using Raman spectroscopy and electron microscopy, we demonstrate that initial thermal annealing of SWNT significantly improves their dispersion in PS. In dielectric measurements, the annealed SWNT/PS composites show higher electrical conductivity and a lower percolation threshold (less than 0.3 wt%) than the raw SWNT/PS composites, which provides further evidence of good dispersion of the annealed SWNT in PS. Raman spectra of composites under tension show good transfer of an applied stress from the polymer matrix to SWNT. However, mechanical moduli of the annealed SWNT/PS composites are only increased slightly. The reason for this discrepancy remains unclear.

Resonant excitation of surface plasmons of a metal or metal-coated tip is crucial for achieving high enhancement of an optical signal with apertureless near-field optics. However, it remains a challenge to measure the optical spectrum of a tip with sub-wavelength dimensions. We present a technique based on total internal reflection microscopy to measure the optical properties of tips. A dependence of the optical resonance on the metal deposited is shown for silver-coated and gold-coated tips. These tips were also used to measure the tip-enhanced Raman spectra of silicon and a polymer blend of poly(3,4-ethylenedioxythiophene) and poly(styrenesulfonate) (PEDOT/PSS) at 514.5 and 647 nm incident wavelengths. Qualitative agreement was observed between the tip-enhanced Raman spectra and the optical resonance of the tip measured with the technique developed.

We describe an apertureless near-field Raman spectroscopy setup that has successfully produced substantial enhancements for a wide variety of samples and achieved a high contrast. The tremendous potential of tip-enhanced Raman spectroscopy (TERS) for nanoscale chemical characterization has been demonstrated by various groups by measuring organic dyes, biological molecules, single-walled carbon nanotubes and silicon. Keys to rapid advances in the application of TERS to pressing scientific problems include the optimization of the method to achieve greater reproducibility and greater enhancement factors if possible, but more importantly, greater imaging contrast. Using a side-illumination geometry, we demonstrate reproducible enhancements of the Raman signal per volume on the order of 103–104 using silver- and gold-coated tips on various molecular, polymeric and semiconducting materials as well as on carbon nanotubes. We have experimentally verified localization of the enhancement to a depth of ∼20 nm. Most importantly, optimization of the polarization geometry makes possible a contrast between the near-field and far-field signals of 900% in the case of silicon—a level that makes the technique attractive for various applications. Copyright © 2005 John Wiley & Sons, Ltd.

Analysis of Raman and neutron scattering spectra of lysozyme demonstrates that the protein dynamics follow the dynamics of the solvents glycerol and trehalose over the entire temperature range measured 100-350 K. The protein's fast conformational fluctuations and low-frequency vibrations and their temperature variations are very sensitive to behavior of the solvents. Our results give insight into previous counterintuitive observations that protein relaxation is stronger in solid trehalose than in liquid glycerol. They also provide insight into the effectiveness of glycerol as a biological cryopreservant.

For a range of applications, polymers are now being patterned into nanometer-sized features. In these applications, the robust mechanical properties of the nanostructures are critical for performance and stability. Brillouin light scattering is presented as a nondestructive, noncontact tool used to quantify the elastic constants in such nanostructures. We demonstrate this through a series of thin films and parallel ridges and spacings (gratings) with ridge widths ranging from 180 to 80 nm. For the set of films and structures presented here, the room-temperature elastic moduli did not change with decreasing film thickness or grating ridge width, and this implied that one-dimensional and two-dimensional confinement-induced changes of the mechanical properties were not significant down to feature sizes of 80 nm. Additionally, Brillouin spectra of submicrometer gratings revealed new modes not present in the spectra of thin films. The origin of these new modes remains unclear. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1106–1113, 2004

Elastic and relaxational properties of (NaPO3)(1−x)(Al(PO3)3)x melts and glasses have been studied for x=0, 0.03, 0.06, 0.15, 0.60, and T=293–1433 K. Brillouin light scattering as well as ultrasound were used. The data were carefully analyzed using viscoelastic theory, with emphasis on the effect of added Al(PO3)3, and on searching for a fast relaxation channel (besides the α-relaxation common to glass formers). The fast process is present for x⩾0.03, and the T-dependence of the relative weight of both processes in the melts is derived. The replacement of Na+ by Al3+ increases the high-frequency LA sound velocity drastically, due to a twofold increase of shear modulus. Comparison with the shear viscosity is made. Viscosity and thermodynamic data are used for deriving an estimate of the size of the regions active in the slow relaxation process. Possible origins of the relaxation processes are discussed.

The mechanism of protein stabilization by glassy solvents is not entirely clear, and the stabilizer effective for a given protein is often discovered empirically. We use low frequency Raman spectroscopy as an effective tool to directly evaluate the ability of different solvents to suppress the conformational fluctuations that can lead to both protein activity and denaturation. We demonstrate that while trehalose provides superior suppression at high temperatures, glycerol is more effective at suppressing protein dynamics at low temperatures. These results suggest that viscosity of the solvent is not the only parameter important for biopreservation. It is also shown that glycerol and water enhance the high temperature conformational fluctuations relative to dry lysozyme, which explains the lower melting temperatures Tm in the hydrated protein and protein formulated in glycerol.

Changes in the fast dynamics of polybutadiene (PB) with molecular weight and molecular architecture have been investigated by light and neutron scattering spectroscopy. Differences observed in the fast dynamics of various molecules correlate with differences seen in the value of the glass-transition temperature (Tg). The segmental and fast dynamics as well as the value of Tg are dependent on the total molecular weight of the molecule but independent of its architecture. In other words, the dynamics of PB depend on the number of segments in the molecule but do not show a significant dependence on how the segments are connected (molecular topology), even for arm molecular weights commensurate with the entanglement molecular weight. Literature data for the Tg's of highly branched, phenolic-terminated dendritic poly(benzyl ethers) of various core structures exhibit the same trend. There is no explanation for why the segmental motion appears to be sensitive to the total molecular weight of the molecule but is independent of its architecture. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2431–2439, 2002

Proteins are often dissolved in viscous glass-forming solvents to provide thermal stability and preserve biochemical activity. However, the mechanisms by which this preservation is achieved are unclear. This issue of biopreservation is undoubtedly affected by both thermodynamic and dynamic parameters. The latter parameters will control the rate of conformational transitions of the protein that accompany biological activity. In the present communication we observe variations of local conformational motions of lysozyme in different solvents by using low-frequency Raman spectroscopy. We demonstrate that at low temperatures liquid glycerol provides a stronger suppression of the fast conformational motions of the protein than glassy trehalose. This demonstrates that solvent viscosity is not the only parameter that controls protein dynamics, and details of the protein–solvent interactions might be important in the biopreservation process.

Light scattering spectra of lysozyme dissolved in glycerol are analyzed over broad ranges in frequency and temperature. It is shown that the dynamic transition observed earlier in a lysozyme/glycerol sample at T∼270 K [Biophys. J. 79 (2000) 2728] is related to the appearance of a slow relaxation process in the GHz frequency window. It is also pointed out that the dynamic transition in the lysozyme/glycerol system happens at a temperature very close to the dynamic transition temperature of bulk glycerol. These results support the idea that biopolymers are `slaves' of solvents and that the latter controls the dynamic transition.

Relaxation processes in polymethylmethacrylate were investigated using light scattering and mechanical relaxation techniques. The acoustic attenuation data cover the frequency range from 1 Hz to 17 GHz and the light scattering from 0.5 to 10 000 GHz. Analysis of the data in a broad temperature range (80–350 K) shows that the model of the asymmetric double-well potentials, traditionally used for description of the acoustic attenuation in glasses, cannot describe all the data consistently. It is shown that assuming an additional relaxation in GHz region with a constant loss spectrum provides a good agreement of the model with experimental data.

The low-frequency vibrations of the Boson peak are observed with inelastic neutron and Raman scattering in a homologous series of polycarbonate copolymers. In accordance with the notion that the Boson peak is predominantly an acoustic phenomenon, the Boson peak energy is found to correlate with the velocity of sound. However, a striking inverse correlation is observed between the Boson peak energy and the average size of the unoccupied volume elements (approximately 5-6 A in diameter) evidenced by positron annihilation lifetime spectroscopy (PALS). The apparent correlation between the Boson peak energy and PALS data is discussed in terms of a relationship between the elastic modulus and the electron density heterogeneities.

A dynamic transition at temperatures ∼200–230K is observed in manyhydrated bio-polymers. It shows up as a sharp increase of the mean-squaredatomic displacements above this temperature range. We present neutronscattering data of DNA at different levels of hydration. The analysis showsthat the dynamic transition in DNA is related to a slow relaxation processin the MHz-GHz frequency range. This slow relaxation process iscompletely suppressed in the dry DNA sample where no dynamic transitionwas observed. The nature of the slow process is discussed. We ascribe it toa global relaxation of DNA molecule that involves cooperative motion ofmany base-pairs and backbone.

There are many speculations about the dynamic transition observed in hydrated bio-polymers at temperatures T ∼ 200 – 230 K being an important factor for enabling of their functions. The transition shows up as a sharp increase of atomic mean-squared displacements above this temperature. The nature of the dynamic transition is not yet clear. Using inelastic neutron scattering we show in this Note that the transition in DNA is related to the appearance of a slow relaxation process. Decrease in the hydration level suppresses the process and the dynamic transition. It is found that, in terms of dynamics, the decrease in water content is similar in effect to a decrease in temperature. The obtained results support the idea that the dynamic transition is mediated by the water of hydration since bulk water has a dynamic transition around the same temperature.

We compare in this report the Brillouin spectra of transverse (TA) phonons in two very different glass-forming systems above the glass transition temperature T g. The first system is the fragile molecular van der Waals liquid m-tricresyl phosphate (mTCP), while the other is the (mainly) ionic salt melt mixture (NaPO3)0.94(Al(PO3)3)0.06, which is of intermediate fragility. The depolarized spectra of mTCP show a pronounced orientational line beside the TA modes. We analyse the spectra using the theoretical ansatz (Dreyfus et al., 1998, Europhys. Lett., 42, 55) which produces the TA spectral shape from a rotation-translation coupling mechanism. The salt melt gives rise to only a weak unresolved central line. The spectral shapes of the phonons are similar as predicted by the ansatz given in Dreyfus et al. (1998). We believe we see here, for the first time experimentally, a transverse line shape, which consists of a propagating part, as usual, but also shows a ‘Mountain’-like non-propagating part, whi...

The structure of glasses in the system As2Se3–CuI have been investigated using X-ray diffraction, Raman and optical spectroscopy. From the width of first sharp diffraction peak (FSDP), the correlation length (Rc) was calculated. While Rc changes with concentration of the CuI content, the position of the FSDP is nearly independent on concentration. The slope of the absorption edge and the transmission in near IR region changes drastically with addition of CuI to glassy As2Se3. The Raman spectra of the glasses show only vibrational modes of the AsSe3 pyramids. Results support a model in which the network of glassy As2Se3 is destroyed by chemically non-reacting CuI-molecules.