Self-Patterning Tetrathiafulvalene Crystalline Films.

Tetrathiafulvalene (TTF) crystals grown from the melt are organized as spherulites in which helicoidal fibrils growing radially from the nucleation center twist in concert with one another. Alternating bright and dark concentric bands are apparent when films are viewed between crossed polarizers, indicating an alternating pattern of crystallographic faces exposed at the film surface. Band-dependent reorganization of the TTF crystals was observed during exposure to methanol vapor. Crystalline growth appears on bright bands at the expense of the dark bands. After a 24 h period of exposure to methanol vapor, the original spherulites were completely restructured, and the films comprise isolated, concentric circles of crystallites whose orientations are determined by the initial TTF crystal fibril orientation. While the surface of these outgrowths appears faceted and smooth, cross-sectional SEM images revealed a semiporous inner structure, suggesting solvent-vapor-induced recrystallization. Collectively, these results show that crystal twisting can be used to rhythmically redistribute material. Crystal twisting is a common and often controllable phenomenon independent of molecular or crystal structure and therefore offers a generalizable path to spontaneous pattern formation in a wide range of materials.

Parallel-Disk Viscometry of a Viscoplastic Hydrogel: Yield Stress and Other Parameters of Shear Viscosity and Wall Slip.

The rheology, i.e., the flow and deformation properties, of hydrogels is generally a very important consideration for their functionality. However, the accurate characterization of their rheological material functions is handicapped by their ubiquitous viscoplasticity and associated wall slip behavior. Here a parallel-disk viscometer was used to characterize the shear viscosity and wall slip behavior of a crosslinked poly(acrylic acid) (PAA) carbomer hydrogel (specifically Carbopol® at 0.12% by weight in water). It was demonstrated that parallel-disk viscometry, i.e., the steady torsional flow in between two parallel disks, can be used to unambiguously determine the yield stress and other parameters of viscoplastic constitutive equations and wall slip behavior. It was specifically shown that torque versus rotational speed information, obtained from parallel-disk viscometry, was sufficient to determine the yield stress of a viscoplastic hydrogel. Additional gap-dependent data from parallel-disk viscometry could then be used to characterize the other parameters of the shear viscosity and wall slip behavior of the hydrogel. To investigate the accuracy of the parameters of shear viscosity and apparent wall slip that were determined, the data were used to calculate the torque values and the velocity distributions (using the lubrication assumption and parallel plate analogy) under different flow conditions. The calculated torques and velocity distributions of the hydrogel agreed very well with experimental data collected by Medina-Bañuelos et al., 2021, suggesting that the methodologies demonstrated here provide the means necessary to understand in detail the steady flow and deformation behavior of hydrogels. Such a detailed understanding of the viscoplastic nature and wall slip behavior of hydrogels can then be used to design and develop novel hydrogels with a wider range of applications in the medical and other industrial areas, and for finding optimum conditions for their processing and manufacturing.

Load-bearing biodegradable PCL-PGA-beta TCP scaffolds for bone tissue regeneration.

A biocompatible and biodegradable scaffold with load-bearing ability is required to enhance the repair of bone defects by facilitating the attachment, and proliferation of cells, and vascularization during new bone formation. However, it is challenging to maintain the porosity and biodegradability, as well as mechanical properties (especially compressive strength), at the same time. Therefore, in the present work, a biodegradable composite structure of poly(caprolactone) (PCL) was designed using compression molding with varying amounts of poly(glycolic acid) (PGA) (25, 50, 75 wt%) and fixed amount (20 wt%) of beta tricalcium phosphate (beta TCP). It was hypothesized that the fabricated composite structure will develop porosity during the degradation of the PGA and that the corresponding decrease in mechanical properties will be compensated by new bone formation and ingrowth, in vivo. Accordingly, we have systematically studied the effects of sample composition on time-dependent dissolution and mechanical properties of the PGA/beta TCP scaffolds. The compressive strength increased up to ~92 MPa at 50% compression of the designed PCL-PGA samples. Furthermore, the dissolution rate, as well as weight loss, was observed to increase with an increase in the PGA amount in PCL. Based on the mechanical properties and dissolution data, it is concluded that the PCL-PGA scaffolds with beta TCP can be suitable candidates for bone tissue engineering applications, specifically for the reconstruction of bone defects, where strength and biodegradation are both important characteristics.

Dynamics of the sub-ambient gelation and shearing of solutions of P3HT and P3HT blends towards active layer formation in bulk heterojunction organic solar cells.

Organic solar cells (OSCs) containing an active layer consisting of a nanostructured blend of a conjugated polymer like poly(3-hexylthiophene) (P3HT) and an electron acceptor have the potential of competing against silicon-based photovoltaic panels. However, this potential is largely unfulfilled first due to interrelated production and stability issues of organic solar cells and second due to the unscalable nature of the generally employed spin coating process used for the fabrication of organic solar cells. Furthermore, alternatives to spin coating, especially relying on continuous polymer processing methods like extrusion and coating, cannot be readily applied due to the typically low shear viscosity and elasticity of polymer solutions making up the active layer. Recently, He et al. have reported that the gelation of P3HT with [6,6]-phenyl-C61-butyric acid methyl ester (PC60BM) under sub-ambient conditions can provide a new route to the processing of the active layers of bulk heterojunction solar cells. Furthermore, increases in power conversion efficiencies (PCEs) of the P3HT/PC60BM active layer were determined to be possible under certain shearing and thermal histories of the P3HT/PC60BM gels. Here oscillatory and steady torsional flows were used to investigate the gel formation dynamics of P3HT with a recently proposed non-fullerene acceptor o-IDTBR under sub-ambient conditions and compared with the gelation behavior of P3HT/PC60BM blends. The rheological material functions as well as the gel strengths defined on the basis of linear viscoelastic material functions, characterized via small-amplitude oscillatory shearing, were observed to be functions of the P3HT and o-IDTBR concentrations, the solvent used and the shearing conditions. Overall, the P3HT gels which formed upon quenching to sub-zero temperatures were found to be stable during small-amplitude oscillatory shear (linear viscoelastic range) but broke down even at the relatively low shear rates associated with steady torsional flows, suggesting that the shearing conditions used during the processing of gels of P3HT and blends of P3HT with small molecule acceptors can alter the gel structure, possibly leading to changes in the resulting active layer performance.

Load-bearing biodegradable polycaprolactone-poly (lactic-co-glycolic acid)- beta tri-calcium phosphate scaffolds for bone tissue regeneration.

A biodegradable scaffold with tissue ingrowth and load-bearing capabilities is required to accelerate the healing of bone defects. However, it is difficult to maintain the mechanical properties as well as biodegradability and porosity (necessary for bone ingrowth) at the same time. Therefore, in the present study, polycaprolactone (PCL) and poly(lactic-co-glycolic acid) (PLGA5050) were mixed in varying ratio and incorporated with 20 wt.% ßTCP. The mixture was shaped under pressure into originally non-porous cylindrical constructs. It is envisioned that the fabricated constructs will develop porosity with the time-dependent biodegradation of the polymer blend. The mechanical properties will be sustained since the decrease in mechanical properties associated with the dissolution of the PLGA and the formation of the porous structure will be compensated with the new bone formation and ingrowth. To prove the hypothesis, we have systematically studied the effects of samples composition on the time-dependent dissolution behavior, pore formation, and mechanical properties of the engineered samples, in vitro. The highest initial (of as-prepared samples) values of the yield strength (0.021±0.002 GPa) and the Young's modulus (0.829±0.096 GPa) were exhibited by the samples containing 75 wt.% of PLGA. Increase of the PLGA concentration from 25 wt.% to 75 wt.% increased the rate of biodegradation by a factor of 3 upon 2 weeks in phosphate buffered saline (1× PBS). The overall porosity and the pore sizes increased with the dissolution time indicating that the formation of in-situ pores can indeed enable the migration of cells followed by vascularization and bone growth.

Machine learning metrology of cell confinement in melt electrowritten three-dimensional biomaterial substrates.

Tuning cell shape by altering the biophysical properties of biomaterial substrates on which cells operate would provide a potential shape-driven pathway to control cell phenotype. However, there is an unexplored dimensional scale window of three-dimensional (3D) substrates with precisely tunable porous microarchitectures and geometrical feature sizes at the cell's operating length scales (10-100 µm). This paper demonstrates the fabrication of such high-fidelity fibrous substrates using a melt electrowriting (MEW) technique. This advanced manufacturing approach is biologically qualified with a metrology framework that models and classifies cell confinement states under various substrate dimensionalities and architectures. Using fibroblasts as a model cell system, the mechanosensing response of adherent cells is investigated as a function of variable substrate dimensionality (2D vs. 3D) and porous microarchitecture (randomly oriented, "non-woven" vs. precision-stacked, "woven"). Single-cell confinement states are modeled using confocal fluorescence microscopy in conjunction with an automated single-cell bioimage data analysis workflow that extracts quantitative metrics of the whole cell and sub-cellular focal adhesion protein features measured. The extracted multidimensional dataset is employed to train a machine learning algorithm to classify cell shape phenotypes. The results show that cells assume distinct confinement states that are enforced by the prescribed substrate dimensionalities and porous microarchitectures with the woven MEW substrates promoting the highest cell shape homogeneity compared to non-woven fibrous substrates. The technology platform established here constitutes a significant step towards the development of integrated additive manufacturing-metrology platforms for a wide range of applications including fundamental mechanobiology studies and 3D bioprinting of tissue constructs to yield specific biological designs qualified at the single-cell level.

Segmental bone replacement via patient-specific, three-dimensional printed bioresorbable graft substitutes and their use as templates for the culture of mesenchymal stem cells under mechanical stimulation at various frequencies.

The treatment of large segmental bone defects remains a challenge as infection, delayed union, and nonunion are common postoperative complications. A three-dimensional printed bioresorbable and physiologically load-sustaining graft substitute was developed to mimic native bone tissue for segmental bone repair. Fabricated from polylactic acid, this graft substitute is novel as it is readily customizable to accommodate the particular size and location of the segmental bone of the patient to be replaced. Inspired by the structure of the native bone tissue, the graft substitute exhibits a gradient in porosity and pore size in the radial direction and exhibit mechanical properties similar to those of the native bone tissue. The graft substitute can serve as a template for tissue constructs via seeding with stem cells. The biocompatibility of such templates was tested under in vitro conditions using a dynamic culture of human mesenchymal stem cells. The effects of the mechanical loading of cell-seeded templates under in vitro conditions were assessed via subjecting the tissue constructs to 28 days of daily mechanical stimulation. The frequency of loading was found to have a significant effect on the rate of mineralization, as the alkaline phosphatase activity and calcium deposition were determined to be particularly high at the typical walking frequency of 2 Hz, suggesting that mechanical stimulation plays a significant role in facilitating the healing process of bone defects. Utilization of such patient-specific and biocompatible graft substitutes, coupled with patient's bone marrow cells seeded and exposed to mechanical stimulation of 2 Hz have the potential of reducing significant volumes of cadaveric tissue required, improving long-term graft stability and incorporation, and alleviating financial burdens associated with delayed or failed fusions of long bone defects.

The rheological behavior of a fast-setting calcium phosphate bone cement and its dependence on deformation conditions.

Calcium phosphate cements are osteoconductive biomaterials that are widely used for bone repair and regeneration applications, including spinal fusion, vertebroplasty, khyphoplasty, cranioplasty and periodontal surgeries. The flow and deformation behavior (rheology) and injectability of the calcium phosphate bone cements to the treatment site are governed by the setting kinetics of the cement during which the initially flowable, viscous cement paste transforms into a rigid elastic solid. Here time-dependent development of the linear viscoelastic properties of a brushite-forming calcium phosphate cement are characterized and linked to the mechanism and kinetics of the setting reaction and to the injectability window available during the surgical applications of the cement. The setting kinetics is shown to be a function of the deformation conditions that are utilized in rheological characterization, emphasizing the intimate relationships between setting kinetics, particle to particle network formation and deformation history. Furthermore, the preshearing of the calcium phosphate cement prior to injection and temperature are shown to alter the kinetics of the setting reaction and thus to provide additional degrees of freedom for the tailoring of the rheological behavior and injectability of the calcium phosphate cement.

Nanoporous nanocomposite membranes via hybrid twin-screw extrusion-multijet electrospinning.

Non-woven nanoporous membranes of poly(caprolactone), PCL, incorporated with multi-walled carbon nanotubes, CNTs, could be fabricated via an industrially-scalable hybrid twin screw extrusion and electrospinning process. The utilization of a spinneret with multiple nozzles allowed the increase of the flow rate beyond what is possible with conventional electrospinning using a single nozzle, albeit at the expense of difficulties in the control of the thickness distributions of the nanofibrous membranes. The thickness and orientation distributions and the resulting mechanical properties of the membranes could be modified via changes in voltage, angular velocity of the collector mandrel and separation distance of the collector from the spinneret. The increases in crystallinity due to the presence of the CNTs and the preferential alignment of the nanofibers via rotation of the collecting mandrel led to increases in the tensile properties of the nanoporous membranes. The use of poly(ethylene oxide), PEO, together with PCL, followed by the dissolution of the PEO, rendered the nanofibers themselves nanoporous with typical surface porosity values of around 50% and pore sizes of about 220 nm. The demonstrated versatility of the hybrid twin screw extrusion and electrospinning process and the manipulation of mesh dimensions and properties are indicative of the applicability of the hybrid process for fabrication of nanoporous membranes for myriad diverse industrial applications ranging from water treatment to tissue engineering applications.

Viscoelastic Properties of Dental Pulp Tissue and Ramifications on Biomaterial Development for Pulp Regeneration.

INTRODUCTION: A critical step in biomaterial selection effort is the determination of material as well as the biological properties of the target tissue. Previously, the selection of biomaterials and carriers for dental pulp regeneration has been solely based on empirical experience. METHODS: In this study, first, the linear viscoelastic material functions and compressive properties of miniature pig dental pulp were characterized using small-amplitude oscillatory shear and uniaxial compression at a constant rate. They were then compared with the properties of hydrogels (ie, agarose, alginate, and collagen) that are widely used in tissue regeneration. RESULTS: The comparisons of the linear viscoelastic material functions of the native pulp tissue with those of the 3 hydrogels revealed the gel-like behavior of the pulp tissue over a relatively large range of time scales (ie, over the frequency range of 0.1-100 rps). At the constant gelation agent concentration of 2%, the dynamic properties (ie, storage and loss moduli and the tanδ) of the collagen-based gel approached those of the native tissue. Under uniaxial compression, the peak normal stresses and compressive moduli of the agarose gel were similar to those of the native tissue, whereas alginate and collagen exhibited significantly lower compressive properties. CONCLUSIONS: The linear viscoelastic and uniaxial compressive properties of the dental pulp tissue reported here should enable the more appropriate selection of biogels for dental pulp regeneration via the better tailoring of gelation agents and their concentrations to better mimic the dynamic and compressive properties of native pulp tissue.

Reverse Kebab Structure Formed inside Carbon Nanofibers via Nanochannel Flow.

The morphology of polymers inside a confined space has raised great interest in recent years. However, polymer crystallization within a one-dimensional carbon nanostructure is challenging due to the difficulty of polar solvents carrying polymers to enter a nonpolar graphitic nanotube in bulk solution at normal temperature and pressure. Here we describe a method whereby nylon-11 was crystallized and periodically distributed on the individual graphitic nanocone structure within hollow carbon nanofibers (CNF). Differential scanning calorimetry and X-ray diffraction indicate that the nylon polymer is in the crystalline phase. A mechanism is suggested for the initiation of nanochannel flow in a bulk solvent as a prerequisite condition to achieve interior polymer crystallization. Selective etching of polymer crystals on the outer wall of CNF indicates that both surface tension and viscosity affect the flow within the CNF. This approach provides an opportunity for the interior functionalization of carbon nanotubes and nanofibers for applications in the biomedical, energy, and related fields.

Interfacial load transfer in polymer/carbon nanotube nanocomposites with a nanohybrid shish kebab modification.

Interfacial properties are known to have a critical effect on the mechanical properties of a nanocomposite material system. Here, the interfacial load transfer in a carbon nanotube (CNT)/nylon-11 composite was studied with a CNT/nylon-11 nanohybrid shish kebab (NHSK) structure modification using Raman spectroscopy. Characterization of the polymer crystal in the NHSK using differential scanning calorimetry (DSC) for the first time indicates that the NHSK structure formed a more perfect crystal structure than the bulk polymer. On the basis of transmission electron microscopy and DSC results, a new growth model for the NHSK crystal is hypothesized, indicating the formation of an initial uniform crystal layer on the CNT prior to the crystallization of the kebabs. Characterization of the nanocomposites using Raman spectroscopy, with the samples heated to introduce interfacial shear stress caused by thermal expansion mismatch, found that the D* band of the CNT in the NHSK/nylon-11 composite displayed a more pronounced shift with an increase in temperature, which is attributed to the NHSK structure being more effective at transferring load from the nylon matrix to the nanotube inclusions. The NHSK structure was also used to fabricate composites with two amorphous polymers, polycarbonate and poly(methyl methacrylate), to investigate the load transfer mechanism. It was found that when the compatibility between the polymer in the NHSK structure and the bulk polymer matrix at the molecular level is sufficiently high, the ensuing mechanical interlocking effect further enhances the interfacial load transfer for polymer nanocomposites. Additional mechanical characterization of polymer nanocomposites with 0.1 wt % NHSK reinforcement demonstrates how the moduli and ultimate tensile strength of the nanocomposites can be improved via this NHSK structure.

Factors affecting the rheology and processability of highly filled suspensions.

Suspensions filled with rigid particles at volume-loading levels that approach their maximum packing fraction are widely encountered, especially in the energetics, ceramics, pharmaceutical, magnetics, composites, food, and personal care industries. Highly filled suspensions, regardless of industrial application, exhibit a number of common rheological and processability traits, including viscoplasticity and wall slip, that necessitate special rheometers and appropriate characterization and numerical simulation methods. Furthermore, various factors, including the dispersion and distribution of the particles and their agglomerates, the entrainment of air, the filtration-based migration of the binder phase, and the shear-induced migration of particles, play important roles and must be considered in the design and optimization of manufacturing operations for processing of highly filled suspensions.

A nanobursa mesh: a graded electrospun nanofiber mesh with metal nanoparticles on carbon nanotubes.

A new type of material, a "nanobursa" mesh (from "bursa" meaning "sac or pouch"), is introduced. This material consists of sequential layers of porous polymeric nanofibers encapsulating carbon nanotubes, which are functionalized with different metal nanoparticles in each layer. The nanobursa mesh is fabricated via a novel combination of twin-screw extrusion and electrospinning. Use of this hybrid process at industrially-relevant rates is demonstrated by producing a nanobursa mesh with graded layers of Pd, Co, Ag, and Pt nanoparticles. The potential use of the fabricated nanobursa mesh is illustrated by modeling of catalytic hydrocarbon oxidation.

Laminin Functionalized Biomimetic Nanofibers For Nerve Tissue Engineering.

Large-gap peripheral nerve injuries present a significant challenge for nerve regeneration due to lack of suitable grafts, insufficient cell penetration, and repair. Biomimetic nanofibrous scaffolds, functionalized on the surface with extracellular matrix proteins, can lead to novel therapies for repair and regeneration of damaged peripheral nerves. Here, nanofibrous scaffolds electrospun from blends of poly(caprolactone) (PCL) and chitosan were fabricated. Taking advantage of the amine groups on the chitosan, the surface of the scaffolds were functionalized with laminin by carbodiimide based crosslinking. Crosslinking allowed laminin to be attached to the surfaces of the PCL-chitosan nanofibers at relatively high concentrations that were not possible using conventional adsorption methods. The nanofibrous meshes were tested for wettability, mechanical properties and cell attachment and proliferation. Blending of chitosan with PCL provided more favorable surfaces for attachment of Schwann cells due to the reduction of the contact angle in comparison to neat PCL. Proliferation rates of Schwann cells grown on PCL-chitosan scaffolds with crosslinked laminin were significantly higher than the rates for PCL-chitosan nanofibrous matrices with adsorbed laminin. PCL-chitosan scaffolds with modified surfaces via crosslinking of laminin could potentially serves as versatile substrates with excellent mechanical and surface properties for in vivo cell delivery for nerve tissue engineering applications.

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.

Radially and axially graded multizonal bone graft substitutes targeting critical-sized bone defects from polycaprolactone/hydroxyapatite/tricalcium phosphate.

Repair and regeneration of critical sized defects via the utilization of polymeric bone graft substitutes are challenges. Here, we introduce radially and axially graded multizonal bone graft substitutes fabricated from polycaprolactone (PCL), and PCL biocomposites with osteoconductive particles, that is, hydroxyapatite (HA), and ß-tricalcium phosphate (TCP). The novel bone graft substitutes should provide a greater degree of freedom to the orthopedic surgeon especially for repair of critically sized bone defects. The modulus of the graft substitute could be tailored in the axial direction upon the systematic variation of the HA/TCP concentration, while in the radial direction the bone graft substitute consisted of an outer layer with high stiffness, encapsulating a softer core with greater porosity. The biocompatibility of the bone graft substitutes was investigated using in vitro culturing of human bone marrow-derived stromal cells followed by the analysis of cell proliferation and differentiation rates. The characterization of the tissue constructs included the enzymatic alkaline phosphates (ALP) activity, microcomputed tomography imaging, and polymerase chain reaction analysis involving the expressions of bone markers, that is, Runx2, ALP, collagen type I, osteopontin, and osteocalcin, overall demonstrating the differentiation of bone marrow derived stem cells (BMSCs) via osteogenic lineage and formation of mineralized bone tissue.

Unitary bioresorbable cage/core bone graft substitutes for spinal arthrodesis coextruded from polycaprolactone biocomposites.

A unitary bioresorbable cage/core bone graft substitute consisting of a stiff cage and a softer core with interconnected porosity is offered for spinal arthrodesis. Polycaprolactone, PCL, was used as the matrix and hydroxyapatite, HA, and ß-tricalcium phosphate, TCP, were used in the formulation of the cage layer to impart modulus increase and osteoconductivity while the core consisted solely of PCL. The crystallinity, biodegradation rate (under accelerated conditions) and mechanical properties, i.e., the uniaxial compression, relaxation modulus upon step compression and cyclic compressive fatigue properties, of the co-extruded cage/core bone graft substitutes could be manipulated by changes in the concentration of HA/TCP in the cage layer. The cyclic fatigue behavior of the cage/core bone graft substitutes were also compared to the behavior of bovine vertebral cancellous bone characterized under similar testing conditions. The biocompatibility of the cage/core bone graft substitutes were assessed via in vitro culturing of human bone marrow derived stromal cells, BMSCs. The cell proliferation rates, time dependencies of the alkaline phosphates (ALP) activity and the expressions of bone markers, i.e., Runx2, ALP, collagen type I, osteopontin and osteocalcin, and the collected µ-CT images demonstrated the differentiation of BMSCs via osteogenic lineage and formation of mineralized bone tissue to indicate the biocompatibility of the cage/core bone graft substitutes.

In vitro analysis and mechanical properties of twin screw extruded single-layered and coextruded multilayered poly(caprolactone) scaffolds seeded with human fetal osteoblasts for bone tissue engineering.

In vitro culturing and mechanical properties of three types of three-dimensional poly(caprolactone) scaffolds with interconnecting open-foam networks are reported. The scaffolds targeted bone tissue regeneration and were fabricated using twin screw extrusion and coextrusion techniques, for continuous mixing/shaping and formation of single or multilayers with distinct and tailorable porosities and pore sizes. Human fetal preosteoblastic cells, hFOB, were cultured on the extruded and coextruded scaffolds under osteogenic supplements and the samples of the resulting tissue constructs were removed and characterized for cell viability and proliferation using the MTS assay, differentiation, and mineralized matrix synthesis via the alkaline phosphatase, ALP, activity and Alizarin Red staining and cell migration using confocal microscopy and scanning electron microscopy. The hFOB cells formed a confluent lining on scaffold surfaces, migrated to the interior and generated abundant extracellular matrix after 2 weeks of culturing, indicative of the promise of such scaffolds for utilization in tissue engineering. The scaffolds and tissue constructs exhibited compressive fatigue behavior that was similar to that of cancellous bone, suggesting the suitability of their use as bone graft substitutes especially for repair of critical-sized defects or nonunion fractures.

Biomass pretreatment strategies via control of rheological behavior of biomass suspensions and reactive twin screw extrusion processing.

Twin screw extrusion based pretreatment of biomass is an attractive option due to its flexibility to carry out chemical reactions under relatively high stresses, temperatures and pressures. However, extrusion processes are rarely utilized in biomass pretreatment because such processing is constrained by rheological behavior of typical biomass suspensions. Without the manipulation of their rheological behavior, biomass suspensions become unprocessable within the extruder at modest biomass concentrations. Here it is demonstrated that gelation agents can render biomass suspensions processable. Specifically, carboxy methyl cellulose, CMC, could be used in conjunction with alkaline pretreatment of hardwood-type biomass and enabled separation of lignin from cellulose fibers. Furthermore, recycled black liquor, obtained upon pretreatment, was determined to be as effective as CMC for rendering biomass suspensions flowable by again facilitating the concomitant application of high shearing stresses and chemical treatment for the pretreatment of the biomass in the twin screw extruder.