Scientific publications

Abstract Switchable underwater adhesion can be useful for numerous applications, but is extremely challenging due to the presence of water at the contact interface. Here, deformable cupped microstructures (diameter typically 100 µm, rim thickness 5 µm) are reported that can switch between high (≈1 MPa) and low (<0.2 MPa) adhesion strength by adjusting the retraction velocity from 100 to 0.1 µm s–1. The velocity at which the switch occurs is determined by specific design parameters of the cupped microstructure, such as the cup width and angle. The results are compared with theoretical estimates of water penetration into the contact zone and expansion of the cup during retraction. This work paves the way for controlling wet adhesion on demand and may inspire further applications in smart adhesives.

Thiol-maleimide and thiol-vinylsulfone cross-linked hydrogels are widely used systems in 3D culture models, in spite of presenting uncomfortable reaction kinetics for cell encapsulation: too fast (seconds for thiol-maleimide) or too slow (minutes-hours for thiol-vinylsulfone). Here, we introduce the thiol-methylsulfone reaction as alternative cross-linking chemistry for cell encapsulation, particularized for PEG-hydrogels. The thiol-methylsulfone reaction occurs at high conversion and at intermediate reaction speed (seconds-minutes) under physiological pH range. These properties allow easy mixing of hydrogel precursors and cells to render homogeneous cell-laden gels at comfortable experimental time scales. The resulting hydrogels are cytocompatible and show comparable hydrolytic stability to thiol-vinylsulfone gels. They allow direct bioconjugation of thiol-derivatized ligands and tunable degradation kinetics by cross-linking with degradable peptide sequences. 3D cell culture of two cell types, fibroblasts and human umbilical vein endothelial cells (HUVECs), is demonstrated.

Hydroxyapatite coatings need similarly shaped splats as building blocks and then a homogeneous microstructure to unravel the structural and chemical hierarchy for more refined improvements to implant surfaces. Coatings were thermally sprayed with differently sized powders (20–40, 40–63 and 63–80 µm) to produce flattened homogeneous splats. The surface was characterized for splat shape by profilometry and Atomic force microscopy (AFM), crystal size by AFM, crystal orientation by X-ray diffraction (XRD) and structural variations by XRD. Chemical composition was assessed by phase analysis, but variations in chemistry were detected by XRD and Raman spectroscopy. The resulting surface electrical potential was measured by Kelvin probe AFM. Five levels of structural hierarchy were suggested: the coating, the splat, oriented crystals, alternate layers of oxyapatite and hydroxyapatite (HAp) and the suggested anion orientation. Chemical hierarchy was present over a lower range of order for smaller splats. Coatings made from smaller splats exhibited a greater electrical potential, inferred to arise from oxyapatite, and supplemented by ordered OH− ions in a rehydroxylated surface layer. A model has been proposed to show the influence of structural hierarchy on the electrical surface potential. Structural hierarchy is proposed as a means to further refine the properties of implant surfaces.

Abstract Space cooling and heating currently result in huge amounts of energy consumption and various environmental problems. Herein, a switching strategy is described for efficient energy-saving cooling and heating based on the dynamic cavitation of silicone coatings that can be reversibly and continuously tuned from a highly porous state to a transparent solid. In the porous state, the coatings can achieve efficient solar reflection (93%) and long-wave infrared emission (94%) to induce a subambient temperature drop of about 5 °C in hot weather (≈35 °C). In the transparent solid state, the coatings allow active sunlight permeation (95%) to induce solar heating to raise the ambient temperature from 10 to 28 °C in cold weather. The coatings are made from commercially available, cheap materials via a facile, environmentally friendly method, and are durable, reversible, and patternable. They can be applied immediately to various existed objects including rigid substrates.

Most everyday surfaces are randomly rough and self-similar on sufficiently small scales. We investigated the tactile perception of randomly rough surfaces using 3D-printed samples, where the topographic structure and the statistical properties of scale-dependent roughness were varied independently. We found that the tactile perception of similarity between surfaces was dominated by the statistical micro-scale roughness rather than by their topographic resemblance. Participants were able to notice differences in the Hurst roughness exponent of 0.2, or a difference in surface curvature of 0.8 $$\hbox {mm}^{-1}$$mm-1for surfaces with curvatures between 1 and 3 $$\hbox {mm}^{-1}$$mm-1. In contrast, visual perception of similarity between color-coded images of the surface height was dominated by their topographic resemblance. We conclude that vibration cues from roughness at the length scale of the finger ridge distance distract the participants from including the topography into the judgement of similarity. The interaction between surface asperities and fingertip skin led to higher friction for higher micro-scale roughness. Individual friction data allowed us to construct a psychometric curve which relates similarity decisions to differences in friction. Participants noticed differences in the friction coefficient as small as 0.035 for samples with friction coefficients between 0.34 and 0.45.

One of the contentious issues associated with the high-cycle fatigue of Nitinol, a nominally equiatomic alloy of nickel and titanium, is the claim that increasing the applied mean strain can increase, or at least have no negative impact, on the fatigue lifetime, in conflict with reported behavior for the vast majority of other metallic materials. To investigate this in further detail, cyclic fatigue tests in bending were carried out on electropolished medical grade Nitinol at 37 °C for lives of up to 400 million cycles of strain involving various levels of the mean strain. A constant life model was developed through statistical analysis of the fatigue data, with 90% reliability at a confidence level of 95% on the effective fatigue strain. Our results show that the constant life diagram, a plot of strain amplitude versus mean strain, is monotonic yet nonlinear for lives of 400 million cycles of fatigue loading. Specifically, we find that in contradiction to the aforementioned claim, the strain amplitude limit at zero mean strain is 0.55% to achieve a 400 million cycle lifetime, at 90% reliability with 95% confidence; however, to achieve the same lifetime, reliability and confidence level in the presence of a 3% or more mean strain, the required strain amplitude limit is decreased by over a factor of three to 0.16%. Moreover, for mean strains from 3% to 7%, the strain amplitude limit that allows a 400 million cycle lifetime, at 90% reliability with 95% confidence, is ~ 0.16%, and essentially independent of mean strain. We conclude that the debatable claim that an increase in the applied mean strain can increase the fatigue life of Nitinol components is not supported by the current data.

A new series of amphiphilic block copolymers has been prepared by ring opening polymerization (ROP) of cyclic carbonates using PEG as initiator. The light responsive unit [7–(diethylaminocoumarin)–4–yl]methyl ester has been introduced by a modular and versatile supramolecular approach, while a reference covalent copolymer has been synthesized for the shake of comparison. Synthesized copolymers showed monomodal narrow distributions and were able to self-assemble into spherical micelles when dispersed in water. UV irradiation allowed us the modification of the self-assemblies morphology, as proved by means of fluorescence spectroscopy, dynamic light scattering (DLS) and transmission electron microscopy (TEM). Both the supramolecular and covalent functionalized block copolymers were able to encapsulate small fluorescent probes as payload and to release them upon UV and NIR irradiation.

Optical polymers cover only a rather narrow range of optical properties. This is a limiting factor for the design of polymer-based optical systems such as smartphone cameras. Moreover, it also poses a problem for femtosecond two-photon lithography, which is a state-of-the-art technology to 3D print high-quality optics from photopolymers. To overcome the limitations of conventional polymers, we introduce nano-inks based on the commonly used photopolymers IP-DIP and IP-S as polymer matrix and zirconium dioxide (ZrO2) nanoparticles. We show that the refractive index and dispersion of these nano-inks can be purposefully tailored by varying the constituent materials and the volume fraction of the nanoparticles. Furthermore, we demonstrate the suitability of our nano-inks for optical applications by 3D printing single micro-lenses and a multi-material achromatic Fraunhofer doublet. Our findings confirm that nanocomposites expand the range of optical properties that are accessible for polymer-based systems and allow for the design of tailored optical materials.

A series of ultrathin, homogenous gold nanoparticle (AuNP) substrates for surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) were prepared using a simple air/water interface approach. These SALDI substrates enabled soft ionization and provided significant improvements in terms of signal intensities and reduced background levels in comparison to other AuNP morphologies for different analytes such as fatty acids, peptides, amino acids, saccharides, and drugs. Through different microscopic and spectroscopic methods, we determined that the packing homogeneity of the [AuNP]n substrates played a vital role in the efficiency of the SALDI process. We demonstrated that the signal intensities of the investigated analytes were readily optimized by manipulating the thickness of the [AuNP]n substrates. The desorption/ionization efficiency increased as a function of the number of layers and then reached a saturation point. The optimized [AuNP]n substrates not only exhibited high SALDI-MS desorption/ionization efficiencies but also showed excellent reproducibilities of the analyte signals.

Tofacitinib (TFB), a Janus kinase inhibitor, has shown excellent success off-label in treating various dermatological diseases, especially alopecia areata (AA). However, TFB’s safe and targeted delivery into hair follicles (HFs) is highly desirable due to its systemic adverse effects. Nanoparticles (NPs) can enhance targeted follicular drug delivery and minimize interfollicular permeation and thereby reduce systemic drug exposure. In this study, we report a facile method to assemble the stable and uniform 240 nm TFB loaded squalenyl derivative (SqD) nanoparticles (TFB SqD NPs) in aqueous solution, which allowed an excellent loading capacity (LC) of 20%. The SqD NPs showed an enhanced TFB delivery into HFs compared to the aqueous formulations of plain drug in an ex vivo pig ear model. Furthermore, the therapeutic efficacy of the TFB SqD NPs was studied in a mouse model of allergic dermatitis by ear swelling reduction and compared to TFB dissolved in a non-aqueous mixture of acetone and DMSO (7:1 v/v). Whereas such formulation would not be acceptable for use in the clinic, the TFB SqD NPs dispersed in water illustrated a better reduction in inflammatory effects than plain TFB’s aqueous formulation, implying both encouraging good in vivo efficacy and safety. These findings support the potential of TFB SqD NPs for developing a long-term topical therapy of AA.