Molecular Probing of the Microscopic Pressure at Contact Interfaces.

Obtaining insights into friction at the nanoscopic level and being able to translate these into macroscopic friction behavior in real-world systems is of paramount importance in many contexts, ranging from transportation to high-precision technology and seismology. Since friction is controlled by the local pressure at the contact it is important to be able to detect both the real contact area and the nanoscopic local pressure distribution simultaneously. In this paper, we present a method that uses planarizable molecular probes in combination with fluorescence microscopy to achieve this goal. These probes, inherently twisted in their ground states, undergo planarization under the influence of pressure, leading to bathochromic and hyperchromic shifts of their UV-vis absorption band. This allows us to map the local pressure in mechanical contact from fluorescence by exciting the emission in the long-wavelength region of the absorption band. We demonstrate a linear relationship between fluorescence intensity and (simulated) pressure at the submicron scale. This relationship enables us to experimentally depict the pressure distribution in multiasperity contacts. The method presented here offers a new way of bridging friction studies of the nanoscale model systems and practical situations for which surface roughness plays a crucial role.

Controlling Macroscopic Friction through Interfacial Siloxane Bonding.

Controlling macroscopic friction is crucial for numerous natural and industrial applications, ranging from forecasting earthquakes to miniaturizing semiconductor devices, but predicting and manipulating friction phenomena remains a challenge due to the unknown relationship between nanoscale and macroscopic friction. Here, we show experimentally that dry friction at multiasperity Si-on-Si interfaces is dominated by the formation of interfacial siloxane (Si─O─Si) bonds, the density of which can be precisely regulated by exposing plasma-cleaned silicon surfaces to dry nitrogen. Our results show how the bond density can be used to quantitatively understand and control the macroscopic friction. Our findings establish a unique connection between the molecular scale at which adhesion occurs, and the friction coefficient that is the key macroscopic parameter for industrial and natural tribology challenges.

Super-resolution Fluorescence Imaging of Recycled Polymer Blends via Hydrogen Bond-Assisted Adsorption of a Nile Red Derivative.

A key challenge in the recycling of multilayer plastic films of polyethylene and polyamide, as typically used for food packaging, is to assess and control the phase separation of the two types of polymers in the recycled material, the specifics of which determine the mechanical strength of the recycled material. However, visualizing the polyamide-in-polyethylene domains with conventional fluorescence methods or electron microscopy is challenging. We present a new approach that combines the point accumulation in nanoscale topography (PAINT) super-resolution method with a newly synthesized Nile Red probe (diOHNR) as the fluorescent label. The molecule was modified to undergo a hydrogen bond-assisted interaction with the polyamide phase in the blend due to its two additional hydroxyl groups but preserves the spectral properties of Nile Red. As a result, the localization density of the probe in the PAINT image is 13 times larger at the polyamide phase than at the polyethylene phase, enabling quantitative evaluation of the spatial polyamide/polyethylene distribution down to the nanoscale. The method achieved a spatial resolution of 18.8 nm, and we found that over half of the polyamide particles in a recycled sample were smaller than the optical diffraction limit. Being able to image the blends with nanoscopic resolution can help to optimize the composition and mechanical properties of recycled materials and thus contribute to an increased reuse of plastics.

Targeting Chondroitin Sulphate Synthase 1 (Chsy1) Promotes Axon Growth Following Neurorrhaphy by Suppressing Versican Accumulation.

Versican is a chondroitin sulfate proteoglycan (CSPG), which deposits in perineurium as a physical barrier and prevents the growth of axons out of the fascial boundary. Several studies have indicated that the chondroitin sulfate (CS) chains on versican have several possible functions beyond the physical barrier, including the ability to stabilize versican core protein in the extracellular matrix. As chondroitin sulfate synthase 1 (Chsy1) is a crucial enzyme for CS elongation, we hypothesized that in vivo knockdown of Chsy1 at peripheral nerve lesion site may decrease CS and versican accumulation, and result in accelerating neurite regeneration. In the present study, end-to-side neurorrhaphy (ESN) in Wistar rats was used as an in vivo model of peripheral nerve injury to evaluate nerve regeneration after surgical intervention. The distribution and expression of versican and Chsy1 in regenerating axons after ESN was studied using confocal microscopy and western blotting. Chsy1 was silenced at the nerve lesion (surgical) site using in vivo siRNA transfection. The results indicated that Chsy1 was successfully silenced in nerve tissue, and its downregulation was associated with functional recovery of compound muscle action potential. Silencing of Chsy1 also decreased the accumulation of versican core protein, suggesting that transient treating of Chsy1-siRNA may be an alternative and an effective strategy to promote injured peripheral nerve regeneration.

Molecular Probing of the Stress Activation Volume in Vapor Phase Lubricated Friction.

When two solid objects slide over each other, friction results from the interactions between the asperities of the (invariably rough) surfaces. Lubrication happens when viscous lubricants separate the two surfaces and carry the load such that solid-on-solid contacts are avoided. Yet, even small amounts of low-viscosity lubricants can still significantly lower friction through a process called boundary lubrication. Understanding the origin of the boundary lubricating effect is hampered by challenges in measuring the interfacial properties of lubricants directly between the two surfaces. Here, we use rigidochromic fluorescent probe molecules to measure precisely what happens on a molecular scale during vapor-phase boundary lubrication of a polymer bead-on-glass interface. The probe molecules have a longer fluorescence lifetime in a confined environment, which allows one to measure the area of real contact between rough surfaces and infer the shear stress at the lubricated interfaces. The latter is shown to be proportional to the inverse of the local interfacial free volume determined using the measured fluorescence lifetime. The free volume can then be used in an Eyring-type model as the stress activation volume, allowing to collapse the data of stress as a function of sliding velocity and partial pressure of the vapor phase lubricant. This shows directly that as more boundary lubricant is applied, larger clusters of lubricant molecules become involved in the shear process thereby lowering the friction.

Local Shearing Force Measurement during Frictional Sliding Using Fluorogenic Mechanophores.

When two macroscopic objects touch, the real contact typically consists of multiple surface asperities that are deformed under the pressure that holds the objects together. Application of a shear force makes the objects slide along each other, breaking the initial contacts. To investigate how the microscopic shear force at the asperity level evolves during the transition from static to dynamic friction, we apply a fluorogenic mechanophore to visualize and quantify the local interfacial shear force. When a contact is broken, the shear force is released and the molecules return to their dark state, allowing us to dynamically observe the evolution of the shear force at the sliding contacts. We find that the macroscopic coefficient of friction describes the microscopic friction well, and that slip propagates from the edge toward the center of the macroscopic contact area before sliding occurs. This allows for a local understanding of how surfaces start to slide.

Syndecan-3 contributes to the regulation of the microenvironment at the node of Ranvier following end-to­side neurorrhaphy: sodium image analysis.

Syndecan-3 (SDC3) and Syndecan-4 (SDC4) are distributed throughout the nervous system (NS) and are favourable factors in motor neuron development. They are also essential for regulation of neurite outgrowth in the CNS. However, their roles in the reconstruction of the nodes of Ranvier after peripheral nerve injury (PNI) are still unclear. Present study used an in vivo model of end-to-side neurorrhaphy (ESN) for 1-3 months. The recovery of neuromuscular function was evaluated by grooming test. Expression and co-localization of SDC3, SDC4, and Nav1.6 channel (Nav1.6) at regenerating axons were detected by proximity ligation assay and confocal microscopy after ESN. Time-of-flight secondary ion mass spectrometry was used for imaging ions distribution on tissue. Our data showed that the re-clustering of sodium and Nav1.6 at nodal regions of the regenerating nerve corresponded to the distribution of SDC3 after ESN. Furthermore, the re-establishment of sodium and Nav1.6 correlated with the recovery of muscle power 3 months after ESN. This study suggested syndecans may involve in stabilizing Nav1.6 and further modulate the distribution of sodium at nodal regions after remyelination. The efficiency of sodium re-clustering was improved by the assistance of anionic syndecan, resulting in a better functional repair of PNI.

Directing charge transfer in perylene based light-harvesting antenna molecules.

Directing energy and charge transfer processes in light-harvesting antenna systems is quintessential for optimizing the efficiency of molecular devices for artificial photosynthesis. In this work, we report a novel synthetic method to construct two regioisomeric antenna molecules (1-D2A2 and 7-D2A2), in which the 4-(n-butylamino)naphthalene monoimide energy and electron donor is attached to the perylene monoimide diester (PMIDE) acceptor at the 1- and 7-bay positions, respectively. The non-symmetric structure of PMIDE renders a polarized distribution of the frontier molecular orbitals along the long axis of this acceptor moiety, which differentiates the electron coupling between the donor, attached at either the 1- or the 7-position, and the acceptor. We demonstrate that directional control of the photo-driven charge transfer process has been obtained by engineering the molecular structure of the light-harvesting antenna molecules.

Development of a 3D porous chitosan/gelatin liver scaffold for a bioartificial liver device.

Functional artificial livers (FALs), with embedded hepatocytes that perform the functions of a normal liver, have been developed during the past decades. It is important to note that the liver scaffold, which is a biologically functional core of bioartificial livers, plays a vital role in the bio-cartridge within a bioartificial liver. In this study, a three-dimensional (3D) liver scaffold for in vitro cultures was fabricated by freeze-drying a chitosan/gelatin (CG) solution. A CG scaffold has advantages such as (i) inexpensive and easy-to-make; (ii) easy to fabricate with varying compressive modulus by changing the concentration of glutaraldehyde; (iii) non-cytotoxicity; and (iv) porous structure is similar to extracellular matrix (ECM), thus facilitating hepatocyte adhesion and proliferation. The results revealed that the compressive modulus and maintainability of a CG scaffold was correlated to the increase in glutaraldehyde. Furthermore, hepatocyte viability and hepatic functions showed the best performances with a 0.61% glutaraldehyde-CG scaffold. This CG scaffold not only had higher hepatocyte biocompatibility and mechanical strength, but also maintained hepatic functions and viability in vitro cultures; especially, the mechanical properties of 0.61% glutaraldehyde-CG scaffold were very similar to those in normal liver. The CG scaffold as a liver scaffold may have high potential for further bioartificial liver design in the near future.

Construction of CuO/In2S3/ZnO heterostructure arrays for enhanced photocatalytic efficiency.

Novel one-dimensional (1D) heterostructure arrays composed of CuO nanowire cores, intermediate In2S3 nanostructures, and ZnO nanorod sheaths (i.e. CuO/In2S3/ZnO heterostructure arrays) have been successfully synthesized by a multi-step process. First, single-crystalline CuO nanowires were directly grown on flexible Cu mesh substrates using a one-step annealing process under ambient conditions. Second, In2S3 nanostructures and ZnO nanorods were sequentially grown on the CuO nanowires by a two-step hydrothermal method at low reaction temperature. The morphology, crystal structures, and optical properties of the CuO/In2S3/ZnO heterostructure arrays were studied by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, energy-dispersive spectroscopy, and photoluminescence spectroscopy. The resultant ternary CuO/In2S3/ZnO heterostructure arrays exhibit excellent photocatalytic activity in the photodegradation of rhodamine 6G (R6G) under 10 W UV light irradiation, which is much higher than that of single-component (CuO nanowire arrays) or two-component systems (CuO/In2S3 heterostructure arrays). Furthermore, the reusability test demonstrates that the CuO/In2S3/ZnO heterostructure arrays on the Cu mesh still maintain high photocatalytic activity in the degradation of three kinds of organic pollutants even after five cycles, without any significant decline. These findings provide an insight into the design and synthesis of new CuO-based composites to effectively improve their photocatalytic performance.