Changes in the near edge X-ray absorption fine structure of hybrid organic-inorganic resists upon exposure

We report on the near edge X-ray absorption fine structure (NEXAFS) spectroscopy of hybrid organic-inorganic resists. These materials are nonchemically amplified systems based on Si, Zr, and Ti oxides, synthesized from organically modified precursors and transition metal alkoxides by a sol-gel route and designed for ultraviolet, extreme ultraviolet and electron beam lithography. The experiments were conducted using a scanning transmission X-ray microscope (STXM) which combines high spatial-resolution microscopy and NEXAFS spectroscopy. The absorption spectra were collected in the proximity of the carbon edge (~ 290 eV) before and after in situ exposure, enabling the measurement of a significant photo-induced degradation of the organic group (phenyl or methyl methacrylate, respectively), the degree of which depends on the configuration of the ligand. Photo-induced degradation was more efficient in the resist synthesized with pendant phenyl substituents than it was in the case of systems based on bridging phenyl groups. The degradation of the methyl methacrylate group was relatively efficient, with about half of the initial ligands dissociated upon exposure. Our data reveal that the such dissociation can produce different outcomes, depending on the structural configuration. While all the organic groups were expected to detach and desorb from the resist in their entirety, a sizeable amount of them remain and form undesired byproducts such as alkene chains. In the framework of the materials synthesis and engineering through specific building blocks, these results provide a deeper insight into the photochemistry of resists, in particular for extreme ultraviolet lithography

Biomaterials and engineered microenvironments to control YAP/TAZ-dependent cell behaviour

Mechanical signals are increasingly recognized as overarching regulators of cell behaviour, controlling stemness, organoid biology, tissue development and regeneration. Moreover, aberrant mechanotransduction is a driver of disease, including cancer, fibrosis and cardiovascular defects. A central question remains how cells compute a host of biomechanical signals into meaningful biological behaviours. Biomaterials and microfabrication technologies are essential to address this issue. Here we review a large body of evidence that connects diverse biomaterial-based systems to the functions of YAP/TAZ, two highly related mechanosensitive transcriptional regulators. YAP/TAZ orchestrate the response to a suite of engineered microenviroments, emerging as a universal control system for cells in two and three dimensions, in static or dynamic fashions, over a range of elastic and viscoelastic stimuli, from solid to fluid states. This approach may guide the rational design of technological and material-based platforms with dramatically improved functionalities and inform the generation of new biomaterials for regenerative medicine applications

Poly(organophosphazene)s and the sol–gel technique

We report a survey of the utilization of phosphazene materials in combination with metal alkoxide precursors to form ceramics through the sol–gel technique. Silicon, titanium, zirconium and aluminum three-dimensional oxide networks were exploited for these investigations, while variably functionalized poly[bis­(2,2,2-trifluoroethoxy)phosphazene], poly[bis­(methoxyethoxyethoxy)phosphazene] and poly­[bis(4-hydroxyphenoxy)phosphazene] were used as phosphazene substrates. The resulting new hybrid materials, characterized by SEM, EDAX, DTA, TGA, DSC, DMTA and impedance techniques, showed improved thermal and mechanical stability, and higher ionic conductivity when doped with Li + or Ag + triflates, than those ob-­served for the corresponding original polyphos-­phazenes. Copyright © 1999 John Wiley & Sons, Ltd.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/34747/1/826_ftp.pd

Polysaccharide hydrogels for multiscale 3D printing of pullulan scaffolds

Structurally and mechanically similar to the extracellular matrix (ECM), biomimetic hydrogels offer a number of opportunities in medical applications. However, the generation of synthetic microenvironments that simulate the effects of natural tissue niches on cell growth and differentiation requires new methods to control hydrogel feature resolution, biofunctionalization and mechanical properties. Here we show how these goals can be achieved by using a pullulan-based hydrogel, engineered in composition and server as cell-adhesive hydrogel, 3D photo-printable in dimension, ranging from the macro- to the micro-scale dimensions, and of tunable mechanical properties. For this, we used absorbers that limit light penetration, achieving 3D patterning through stereolithography with feature vertical resolution of 200 μm and with overall dimension up to several millimeters. Furthermore, we report the fabrication of 3D pullulan-modified hydrogels by two-photon lithography, with sub-millimetric dimensions and minimum feature sizes down to some microns. These materials open the possibility to produce multiscale printed scaffolds that here we demonstrate to be inert for cell adhesion, but biologically compatible and easily functionalizable with cell adhesive proteins. Under these conditions, successful cell cultures were established in 2D and 3D. Keywords: Hydrogel, Biomaterials, Polysaccharide, Pullulan, 3D printing, Two photon laser lithography, Mesenchymal stromal cell

Effects of surface topography on growth and osteogenic differentiation of human mesenchymal stem cells

The clinical success of an endosseous artificial implant is related to the quality of its osseointegration with the surrounding living bone. To achieve a stable anchorage, mesenchymal cells, migrating to the implant surface from the surrounding tissue, must differentiate towards mature osteoblasts rather than connective tissue cell types. It is well known that the cell response is affected by the physicochemical parameters of the biomaterial surface, such as surface energy, surface charges or chemical composition. Topography seems to be one of the most crucial physical cues for cells (1). In particular, interactions between mesenchymal stem cells (MSCs) and surfaces with specific micro and nano patterns can stimulate MSCs to produce bone mineral in vitro (2). Herein, stamps reporting different micro and nano features were fabricated in order to obtain several corresponding replicas in a short time through microinjec- tion molding. Then, the effects of the substrate topography on human bone marrowderived MSC adhesion, proliferation, and osteogenic differentiation were investigated in the absence of inductive growth factors. Collectively, our data show that both micro- and nano-structured surfaces possess osteoinductive properties. A relationship between dimensional feature of surface topography and differentiative potential was noted. On the contrary, cell adhesion and proliferation seemed to be unaffected. Further in vivo studies will be carried out to confirm the osteoinductive properties of selected surface geometries

Reprogramming normal cells into tumour precursors requires ECM stiffness and oncogene-mediated changes of cell mechanical properties

Defining the interplay between the genetic events and microenvironmental contexts necessary to initiate tumorigenesis in normal cells is a central endeavour in cancer biology. We found that receptor tyrosine kinase (RTK)–Ras oncogenes reprogram normal, freshly explanted primary mouse and human cells into tumour precursors, in a process requiring increased force transmission between oncogene-expressing cells and their surrounding extracellular matrix. Microenvironments approximating the normal softness of healthy tissues, or blunting cellular mechanotransduction, prevent oncogene-mediated cell reprogramming and tumour emergence. However, RTK–Ras oncogenes empower a disproportional cellular response to the mechanical properties of the cell’s environment, such that when cells experience even subtle supra-physiological extracellular-matrix rigidity they are converted into tumour-initiating cells. These regulations rely on YAP/TAZ mechanotransduction, and YAP/TAZ target genes account for a large fraction of the transcriptional responses downstream of oncogenic signalling. This work lays the groundwork for exploiting oncogenic mechanosignalling as a vulnerability at the onset of tumorigenesis, including tumour prevention strategies

Materiali ibridi organico-inorganici sintetizzati col processo sol-gel

Dottorato di ricerca in ingegneria dei materiali. 8. ciclo. A.a. 1994-95. Tutore M. GuglielmiConsiglio Nazionale delle Ricerche - Biblioteca Centrale - P.le Aldo Moro, 7, Rome; Biblioteca Nazionale Centrale - P.za Cavalleggeri, 1, Florence / CNR - Consiglio Nazionale delle RichercheSIGLEITItal