Herein, we have designed composite SERS-active micro-satellites, which exhibit a dual role: (i) effective probes for determining cellular composition and (ii) optically movable and easily detectable markers. The satellites were synthesized by the layer-by-layer assisted decoration of silica microparticles with metal (gold or silver) nanoparticles and astralen in order to ensure satellite SERS-based microenvironment probing and satellite recognition, respectively. A combination of optical tweezers and Raman spectroscopy can be used to navigate the satellites to a certain cellular compartment and probe the intracellular composition following cellular uptake. In the future, this developed approach may serve as a tool for single cell analysis with nanometer precision due to the multilayer surface design, focusing on both extracellular and intracellular studies.

Polypeptides having secondary structures often undergo self-assembly which can extend over multiple length scales. Poly(γ-benzyl-L-glutamate) (PBLG), for example, folds into α-helices and forms physical organogels, whereas poly(L-glutamic acid) (PLGA at acidic pH) or poly(L-glutamate) (PLG at neutral/basic pH) do not form hydrogels. We explored the gelation of modified PBLG and investigated the deprotection of the carboxylic acid moieties in such gels to yield unique hydrogels. This was accomplished through photo-crosslinking gelation of poly(γ-benzyl-L-glutamate-co-allylglycine) statistical copolymers in toluene, tetrahydrofuran, and 1,4-dioxane. Unlike most polymer-based chemical gels, our gels were prepared from dilute solutions (<20 g L−1, i.e., <2% w/v) of low molar mass polymers. Despite such low concentrations and molar masses, our dioxane gels showed high mechanical stability and little shrinkage; remarkably, they also exhibited a porous fibrillar network. Deprotection of the carboxylic acid moieties in dioxane gels yielded pH responsive and highly absorbent PLGA/PLG-based hydrogels (swelling ratio of up to 87), while preserving the network structure, which is an unprecedented feature in the context of crosslinked PLGA gels. These outstanding properties are highly attractive for biomedical materials.

Chemical composition and fibrillar organization are major determinants of osteonal bone tissue mechanics. However, prominent methodologies commonly applied to investigate mechanical properties of bone on the micro scale are usually not able to concurrently describe both factors. In this study, we used synchrotron X-ray phase nano-tomography, polarized Raman spectroscopy and scanning acoustic microscopy to analyse not only the orientation of the mineralized collagen fibrils in three dimensions, but also the chemical composition and the elastic properties in site-matched regions of human osteonal bone in situ with sub-micron resolution. The aim of this study was to compare the fibrillar orientation patterns identified with the different methodologies and to determine the impact of compositional and organizational characteristics on local elastic properties to gain further insight into the structure-functional relationship of osteonal bone.

Bone material is composed of an organic matrix of collagen fibers and apatite nanoparticles. Previously, vibrational spectroscopy techniques such as infrared (IR) and Raman spectroscopy have proved to be particularly useful for characterizing the two constituent organic and inorganic phases of bone. In this work, we tested the potential use of high intensity synchrotron-based far-IR radiation (50–500 cm−1) to gain new insights into structure and chemical composition of bovine fibrolamellar bone. The results from our study can be summarized in the following four points: (I) compared to far-IR spectra obtained from synthetic hydroxyapatite powder, those from fibrolamellar bone showed similar peak positions, but very different peak widths; (II) during stepwise demineralization of the bone samples, there was no significant change neither to far-IR peak width nor position, demonstrating that mineral dissolution occurred in a uniform manner; (III) application of external loading on fully demineralized bone had no significant effect on the obtained spectra, while dehydration of samples resulted in clear differences. (IV) using linear dichroism, we showed that the anisotropic structure of fibrolamellar bone is also reflected in anisotropic far-IR absorbance properties of both the organic and inorganic phases. Far-IR spectroscopy thus provides a novel way to functionally characterize bone structure and chemistry, and with further technological improvements, has the potential to become a useful clinical diagnostic tool to better assess quality of collagen-based tissues.

The real-time temperature measurement of nanostructured materials is particularly attractive in view of increasing needs of local temperature probing with high sensitivity and resolution in nanoelectronics, integrated photonics, and biomedicine. Light-induced heating and Raman scattering of single-walled carbon nanotubes with adsorbed gold nanoparticles decorating silica microparticles are reported, by both green and near IR lasers. The plasmonic shell is used as nanoheater, while the single-walled carbon nanotubes are Raman active and serve as a thermometer. Stokes and Anti-Stokes Raman spectra of single-walled carbon nanotubes serve to estimate the effective light-induced temperature rise on the metal nanoparticles. The temperature rise is constant with time, indicating stability of the adsorption density. The effective temperatures derived from Stokes and Anti-Stokes intensities are correlated with those measured in a heating stage. The resolution of the thermal experiments in our study was found to be 5-40 K.

Marine mussels utilize multiple bidentate complexes formed by Fe(iii) and DOPA in a mussel adhesive protein (fp-1) to reinforce tough and elastic byssal fibers as a specialized underwater adhesive aid. In this study, mussel-inspired electrospun nanofibers were fabricated using a recombinant mussel adhesive protein (rfp-1), Fe(iii)-DOPA complexes, and polycaprolactone. The mechanical properties of the fabricated nanofibers were reinforced by the Fe(iii)-DOPA complex found in fp-1, which is a key component of the naturally occurring high-performance mussel fiber coating. Experimental results show that the stoichiometry of Fe(iii)-DOPA complexes in the nanofibers could be controlled by buffer pH conditions and the stiffness of the nanofiber mat increased linearly with the concentration of the Fe(iii)-DOPA complexes, as monitored by resonance Raman spectroscopy. This suggests the potential of Fe(iii)-DOPA complexation as an effective strategy for modulating the mechanical properties of nanofibrous biomedical materials by using pH variations.

Reliable and strong surface enhanced Raman scattering (SERS) signatures of intracellular compartments in live NIH3T3 fibroblasts are collected in real time by means of SERS active thin nanofilm (30 nm) on colloidal silica (1.5 μm). Nanofilm is composed of preformed silver nanoparticles in the matrix of polyacrylic acid, protecting against heating (37 °C) in water, or culture medium or phosphate buffered saline aqueous solution. The SERS enhancement factors (EFs) of the order 10(8) allow single biomolecule detection in the native environment of a single live cell. Primary and secondary SERS hot spots of nanofilm are responsible for such high EFs. A slow SERS EF intensity decay occurs over a broader distance of micron silica with nanofilm, not achievable in a common core-shell model (silver nanoparticle coated with a thin silica layer). Extensive local field EFs and SERS EFs are mainly delivered by prolate silver nanoparticles ("rugby-like" shape). This is achieved if an incident field is polarized along the z-axis and the direction of incident polarization and main axis (z) are perpendicular to each other, not observable in water or on gold.