Hydrophobically Modified Isosorbide Dimethacrylates as a Bisphenol-A (BPA)-Free Dental Filling Material.

A series of bio-based hydrophobically modified isosorbide dimethacrylates, with para-, meta-, and ortho- benzoate aromatic spacers (ISBGBMA), are synthesized, characterized, and evaluated as potential dental restorative resins. The new monomers, isosorbide 2,5-bis(4-glyceryloxybenzoate) dimethacrylate (ISB4GBMA), isosorbide 2,5-bis(3-glyceryloxybenzoate) dimethacrylate (ISB3GBMA), and isosorbide 2,5-bis(2-glyceryloxybenzoate) dimethacrylate (ISB2GBMA), are mixed with triethylene glycol dimethacrylate (TEGDMA) and photopolymerized. The resulting polymers are evaluated for the degree of monomeric conversion, polymerization shrinkage, water sorption, glass transition temperature, and flexural strength. Isosorbide glycerolate dimethacrylate (ISDGMA) is synthesized, and Bisphenol A glycerolate dimethacrylate (BisGMA) is prepared, and both are evaluated as a reference. Poly(ISBGBMA/TEGDMA) series shows lower water sorption (39-44 µg/mm3) over Poly(ISDGMA/TEGDMA) (73 µg/mm3) but higher than Poly(BisGMA/TEGDMA) (26 µg/mm3). Flexural strength is higher for Poly(ISBGBMA/TEGDMA) series (37-45 MPa) over Poly(ISDGMA/TEGDMA) (10 MPa) and less than Poly(BisGMA/TEGDMA) (53 MPa) after immersion in phosphate-buffered saline (DPBS) for 24 h. Poly(ISB2GBMA/TEGDMA) has the highest glass transition temperature at 85 °C, and its monomeric mixture has the lowest viscosity at 0.62 Pa·s, among the (ISBGBMA/TEGDMA) polymers and monomer mixtures. Collectively, this data suggests that the ortho ISBGBMA monomer is a potential bio-based, BPA-free replacement for BisGMA, and could be the focus for future study.

Probing the textures of composite skin care formulations using large amplitude oscillatory shear.

Identifying meaningful and measurable rheological parameters that shadow the dynamic shear stresses sustained in the initial application and subsequent spreading of structured cosmetic formulations onto the skin is quite challenging. When applied to non-Newtonian soft solids, traditional oscillatory rheological testing tends to best correlate with the "at-rest" state, or, more fundamentally, with the initial and thermodynamically reversible perturbations in the physiochemical networking that binds components of the amalgamated microstructure. In addition, after yielding, as an applied film is further thinned while spreading on the skin surface, shear rates during flow processes may rapidly and dynamically increase to 104 s⁻¹ , which is a magnitude that is not practically simulated with a standard rotational rheometer. Realistically speaking, it is rare that a single rheological measurement or resultant parameter predicts the sensorial appeal of a complex fluid during the entire scope of a spreading process. Large amplitude oscillatory shear (LAOS) methodology is an augmentation of standard oscillatory rheology, or small amplitude oscillatory shear (SAOS), and delivers a means to dynamically probe the deforming microstructure of a soft solid as it rheologically transitioned from a viscoplastic material to a structured fluid. LAOS rheology was performed on four different prototypes having different skincare textures to produce Bowditch­Lissajous plots (henceforth truncated to Lissajous in the remainder of the document) for subsequent association with previously measured sensorial properties. Insights into the shapes of the curves and their relation to paralleled sensorial analyses are primarily based on the performance of the composite prototypes rather than speculating on the individual contribution of each constituent to the dynamics of the adapting microstructure. Therefore, transitions in the Lissajous trajectories may be used to visually describe changes in the bulk rheology as the physical components of the local viscoelastic environment are controllably sheared. In this work, Lissajous profiles are amassed with smooth and rough surfaces data utilizing standard rheological techniques, including oscillatory SAOS, stress ramps, Brookfield viscometry, and the manifestation of interfacial or complex flow properties, such as wall-slip and shear-banding phenomena. Practical influences on the human stratum corneum, including thermal softening and electrostatic shielding, are also considered. Additionally, outcomes from texture profile analysis are reported and contrasted with the accompanying results. Ultimately, the objective is to make meaningful connections between trends in Lissajous trajectories and paralleled sensorial analyses conducted by a trained expert panel. For the reader, a basic level of rheological knowledge is assumed.

Shell-core bi-layered scaffolds for engineering of vascularized osteon-like structures.

Bottom-up assembly of osteon-like structures into large tissue constructs represents a promising and practical strategy toward the formation of hierarchical cortical bone. Here, a unique two-step approach, i.e., the combination of electrospinning and twin screw extrusion (TSE) techniques was used to fabricate a microfilament/nanofiber shell-core scaffold that could precisely control the spatial distribution of different types of cells to form vascularized osteon-like structures. The scaffold contained a helical outer shell consisting of porous microfilament coils of polycaprolactone (PCL) and biphasic calcium phosphates (BCP) that wound around a hollow electrospun PCL nanofibrous tube (the core). The porous helical shell supported the formation of bone-like tissues, while the luminal surface of nanofibrous core enabled endothelialization to mimic the function of Haversian canal. Culture of mouse pre-osteoblasts (POBs, MC 3T3-E1) onto the coil shells revealed that coils with pitch sizes greater than 135 µm, in the presence of BCP, favored the proliferation and osteogenic differentiation of POBs. The luminal surface of PCL nanofibrous core supported the adhesion and spreading of mouse endothelial cells (ECs, MS-1) to form a continuous endothelial lining with the function similar to blood vessels. Taken together, the shell-core bi-layered scaffolds with porous, coil-like shell and nanofibrous tubular cores represent a new scaffolding technology base for the creation of osteon analogs.

Functionally graded beta-TCP/PCL nanocomposite scaffolds: in vitro evaluation with human fetal osteoblast cells for bone tissue engineering.

The engineering of biomimetic tissue relies on the ability to develop biodegradable scaffolds with functionally graded physical and chemical properties. In this study, a twin-screw-extrusion/spiral winding (TSESW) process was developed to enable the radial grading of porous scaffolds (discrete and continuous gradations) that were composed of polycaprolactone (PCL), beta-tricalciumphosphate (beta-TCP) nanoparticles, and salt porogens. Scaffolds with interconnected porosity, exhibiting myriad radial porosity, pore-size distributions, and beta-TCP nanoparticle concentration could be obtained. The results of the characterization of their compressive properties and in vitro cell proliferation studies using human fetal osteoblast cells suggest the promising nature of such scaffolds. The significant degree of freedom offered by the TSESW process should be an additional enabler in the quest toward the mimicry of the complex elegance of the native tissues.

Multifunctional protein-encapsulated polycaprolactone scaffolds: fabrication and in vitro assessment for tissue engineering.

Here we demonstrate the use of a twin screw extrusion/spiral winding (TSESW) process to generate protein-encapsulated tissue engineering scaffolds. Bovine serum albumin (BSA) was distributed into PCL matrix using both wet and hot melt extrusion methods. The encapsulation efficiency and the time-dependent release rate, as well as the tertiary structure of BSA (via circular dichroism), were investigated as a function of processing method and conditions. Within the relatively narrow processing window of this demonstration study it was determined that the wet extrusion method gave rise to greater stability of the BSA on the basis of circular dichroism data. The rate of proliferation of human fetal osteoblast (hFOB) cells and the rate of mineral deposition were found to be greater for wet extruded scaffolds, presumably due to the important differences in surface topographies (smoother scaffold surfaces upon wet extrusion). Overall, these findings suggest that the twin screw extrusion/spiral winding (TSESW) process offers significant advantages and flexibility in generating a wide variety of non-cytotoxic tissue engineering scaffolds with controllable distributions of porosity, physical and chemical properties and protein concentrations that can be tailored for the specific requirements of each tissue engineering application.

Surface patterning of poly(L-lactide) upon melt processing: in vitro culturing of fibroblasts and osteoblasts on surfaces ranging from highly crystalline with spherulitic protrusions to amorphous with nanoscale indentations.

Large-scale and reproducible manufacturing of scaffolds for tissue engineering applications will necessitate the adoption of methods relying on the processing of the biodegradable polymers directly from the melt. Such solventless processing will give rise to bulk and surface properties that will differ significantly from those generated upon processing from solution-based methods. Thus, detailed understanding of the microstructures that are developed during melt processing and the resulting surface/cell interactions is needed. Here, surfaces of melt-cast poly(L-lactide) (PLLA) were patterned to furnish membrane samples with a wide range of crystallinity and significant differences in surface topographies, ranging from highly crystalline (60%) with spherulitic protrusions at the surface to amorphous with nanoscale indentations. The PLLA membranes were used to culture in vitro mouse 3T3-Swiss albino fibroblast cells and osteoblast-like MC3T3-E1 cells. The growth rates of 3T3 fibroblasts were significantly lower on highly crystalline PLLA membranes with spherulitic protrusions in comparison to crystalline PLLA without spherulitic protrusions and amorphous surfaces with 5-10-nm-deep indentations. However, the differences in the growth rates of osteoblast-like cells cultured on the PLLA membranes with different surface patterns were only marginally different.