Photoswitching Cationic and Radical Polymerizations: Spatiotemporal Control of Thermoset Properties.

The ability to fabricate polymeric materials with spatially controlled physical properties has been a challenge in thermoset manufacturing. To address this challenge, this work takes advantage of a photoswitchable polymerization that selectively incorporates different monomers at a growing chain by converting from cationic to radical polymerizations through modulation of the wavelength of irradiation. By regulating the dosage and wavelength of light applied to the system, the mechanical properties of the crosslinked material can be temporally and spatially tuned. Furthermore, photopatterning can be achieved both on the macroscale and the microscale, enabling precise spatial control of crosslink density that results in high-resolution control over mechanical properties.

Remarkably Weak Anisotropy in Thermal Conductivity of Two-Dimensional Hybrid Perovskite Butylammonium Lead Iodide Crystals.

Two-dimensional (2D) hybrid organic-inorganic perovskites consisting of alternating organic and inorganic layers are a new class of layered structures. They have attracted increasing interest for photovoltaic, optoelectronic, and thermoelectric applications, where knowing their thermal transport properties is critical. We carry out both experimental and computational studies on thermal transport properties of 2D butylammonium lead iodide crystals and find their thermal conductivity is ultralow (below 0.3 W m-1 K-1) with very weak anisotropy (around 1.5) among layered crystals. Further analysis reveals that the unique structure with the preferential alignment of organic chains and complicated energy landscape leads to moderately smaller phonon lifetimes in the out-of-plane direction and comparable phonon group velocities in in-plane and out-of-plane directions. These new findings may guide the future design of novel hybrid materials with desired thermal conductivity for various applications.

Supercompliant and Soft (CH_{3}NH_{3})_{3}Bi_{2}I_{9} Crystal with Ultralow Thermal Conductivity.

In this Letter, we show the phonon dispersion of (CH_{3}NH_{3})_{3}Bi_{2}I_{9} single crystals at 300 K measured by inelastic x-ray scattering. The frequencies of acoustic phonons are among the lowest of crystals. Nanoindentation measurements verified that these crystals are very compliant and considerably soft. The frequency overlap between acoustic and optical phonons results in strong acoustic-optical scattering. All these features lead to an ultralow thermal conductivity. The fundamental knowledge obtained from this study will accelerate the design of novel hybrid materials for energy applications.

The microbial metagenome and bone tissue composition in mice with microbiome-induced reductions in bone strength.

The genetic components of microbial species that inhabit the body are known collectively as the microbiome. Modifications to the microbiome have been implicated in disease processes throughout the body and have recently been shown to influence bone. Prior work has associated changes in the microbial taxonomy (phyla, class, species, etc.) in the gut with bone phenotypes but has provided limited information regarding mechanisms. With the goal of achieving a more mechanistic understanding of the effects of the microbiome on bone, we perform a metagenomic analysis of the gut microbiome that provides information on the functional capacity of the microbes (all microbial genes present) rather than only characterizing the microbial taxa. Male C57Bl/6 mice were subjected to disruption of the gut microbiota (ΔMicrobiome) using oral antibiotics (from 4 to 16 weeks of age) or remained untreated (n = 6-7/group). Disruption of the gut microbiome in this manner has been shown to lead to reductions in tissue mechanical properties and whole bone strength in adulthood with only minor changes in bone geometry and density. ΔMicrobiome led to modifications in the abundance of microbial genes responsible for the synthesis of the bacterial cell wall and capsule; bacterially synthesized carbohydrates; and bacterially synthesized vitamins (B and K) (p < 0.01). Follow up analysis focused on vitamin K, a factor that has previously been associated with bone health. The vitamin K content of the cecum, liver and kidneys was primarily microbe-derived forms of vitamin K (menaquinones) and was decreased by 32-66% in ∆Microbiome mice compared to untreated animals (p < 0.01). Bone mineral crystallinity determined using Raman spectroscopy was decreased in ∆Microbiome mice (p = 0.01). This study illustrates the use of metagenomic analysis to link the microbiome to bone phenotypes and provides preliminary findings implicating microbially synthesized vitamin-K as a regulator of bone matrix quality.

Tuning hardness in calcite by incorporation of amino acids.

Structural biominerals are inorganic/organic composites that exhibit remarkable mechanical properties. However, the structure-property relationships of even the simplest building unit-mineral single crystals containing embedded macromolecules-remain poorly understood. Here, by means of a model biomineral made from calcite single crystals containing glycine (0-7 mol%) or aspartic acid (0-4 mol%), we elucidate the origin of the superior hardness of biogenic calcite. We analysed lattice distortions in these model crystals by using X-ray diffraction and molecular dynamics simulations, and by means of solid-state nuclear magnetic resonance show that the amino acids are incorporated as individual molecules. We also demonstrate that nanoindentation hardness increased with amino acid content, reaching values equivalent to their biogenic counterparts. A dislocation pinning model reveals that the enhanced hardness is determined by the force required to cut covalent bonds in the molecules.

Reduced tissue-level stiffness and mineralization in osteoporotic cancellous bone.

Osteoporosis alters bone mass and composition ultimately increasing the fragility of primarily cancellous skeletal sites; however, effects of osteoporosis on tissue-level mechanical properties of cancellous bone are unknown. Dual-energy X-ray absorptiometry (DXA) scans are the clinical standard for diagnosing osteoporosis though changes in cancellous bone mass and mineralization are difficult to separate using this method. The goal of this study was to investigate possible difference in tissue-level properties with osteoporosis as defined by donor T scores. Spine segments from Caucasian female cadavers (58-92 years) were used. A T score for each donor was calculated from DXA scans to determine osteoporotic status. Tissue-level composition and mechanical properties of vertebrae adjacent to the scan region were measured using nanoindentation and Raman spectroscopy. Based on T scores, six samples were in the Osteoporotic group (58-74 years) and four samples were in the Not Osteoporotic group (65-92 years). The indentation modulus and mineral to matrix ratio (mineral:matrix) were lower in the Osteoporotic group than the Not Osteoporotic group. Mineral:matrix ratio decreased with age (r (2) = 0.35, p = 0.05), and the indentation modulus increased with areal bone mineral density (r (2) = 0.41, p = 0.04). This study is the first to examine cancellous bone composition and mechanical properties from a fracture prone location with osteoporosis. We found differences in tissue composition and mechanical properties with osteoporosis that could contribute to increased fragility in addition to changes in trabecular architecture and bone volume.

Evaluation of strengthening mechanisms in calcite single crystals from mollusk shells.

Biogenic single-crystal calcite is often reported to be harder and tougher than geologic calcite in the form of Iceland spar. However, the mechanistic origins of the superior mechanical properties of the biogenic materials are still debated. We investigate the hardness and modulus of biogenic calcite from the prismatic layer of the mollusk Atrina rigida compared with a pure geologic calcite, Iceland spar. On the {001} face, biogenic calcite is found to be 50-70% harder than geologic calcite. This range is due to the fact that changes in azimuthal angle of the indenter tip lead to a hardness variation of ∼20% in A. rigida but only ∼7% in Iceland spar. The higher hardness and increased anisotropy of biogenic calcite could be accounted for by hardening mechanisms based on hindered dislocation motion rather than crack deflection.

Variations in nanomechanical properties and tissue composition within trabeculae from an ovine model of osteoporosis and treatment.

Osteoporosis and treatment may affect both composition and nanomechanical properties and their spatial distributions within the individual trabeculae of cancellous bone at length scales that cannot be captured by bulk measurements. This study utilized 25 mature adult ewes divided into 5 treatment groups. Four treatment groups were given a dietary model for human high-turnover osteoporosis, and two of these were treated with antiresorptive drugs, either zoledronate (ZOL) or raloxifene (RAL), to examine their effects on bulk tissue properties and nanoscale tissue composition and mechanical properties within trabeculae. Treatment effects were most pronounced at the nanoscale, where RAL increased indentation modulus and hardness throughout trabeculae by 10% relative to the osteoporosis model. In comparison, ZOL increased these properties exclusively at the surfaces of trabeculae (indentation modulus +12%, hardness +16%). Nanomechanical alterations correlated with changes in tissue mineralization, carbonate substitution, crystallinity, and aligned collagen. Despite only minimal changes in bulk tissue tBMD, the nanomechanical improvements within trabeculae with both treatments greatly improved the predicted theoretical bending stiffness of individual trabeculae when idealized as cylindrical struts. Hence, small tissue-level alterations in critical locations for resisting trabecular failure could account for some of the discrepancy between the large reductions in fracture risk and the only modest changes in BMD with antiresorptive treatments.

Improved prediction of rat cortical bone mechanical behavior using composite beam theory to integrate tissue level properties.

Tissue level characteristics of bone can be measured by nanoindentation and microspectroscopy, but are challenging to translate to whole bone mechanical behavior in this hierarchically structured material. The current study calculated weighted section moduli from microCT attenuation values based on tissue level relationships (Z(lin,a) and Z(lin,b)) between mineralization and material properties to predict whole bone mechanical behavior. Z(lin,a) was determined using the equation of the best fit linear regression between indentation modulus from nanoindentation and mineral:matrix ratio from Raman spectroscopy. To better represent the modulus of unmineralized tissue, a second linear regression with the intercept fixed at 0 was used to calculate Z(lin,b). The predictive capability of the weighted section moduli calculated using a tissue level relationship was compared with average tissue level properties and weighted section moduli calculated using an apparent level relationship (Z(exp)) between Young's Modulus and mineralization. A range of bone mineralization was created using vitamin D deficiency in growing rats. After 10 weeks, left femurs were scanned using microCT and tested to failure in 3 point bending. Contralateral limbs were used for co-localized tissue level mechanical properties by nanoindentation and compositional measurements by Raman microspectroscopy. Vitamin D deficiency reduced whole bone stiffness and strength by ∼35% and ∼30%, respectively, but only reduced tissue mineral density by ∼10% compared with Controls. Average tissue level properties did not correlate with whole bone mechanical behavior while Z(lin,a), Z(lin,b), and Z(exp) predicted 54%, 66%, and 80% of the failure moment respectively. This study demonstrated that in a model for varying mineralization, the composite beam model in this paper is an improved method to extrapolate tissue level data to macro-scale mechanical behavior.

Microstructure and nanomechanical properties in osteons relate to tissue and animal age.

Material property changes in bone tissue with ageing are a crucial missing component in our ability to understand and predict age-related fracture. Cortical bone osteons contain a natural gradient in tissue age, providing an ideal location to examine these effects. This study utilized osteons from baboons aged 0-32 years (n=12 females), representing the baboon lifespan, to examine effects of tissue and animal age on mechanical properties and composition of the material. Tissue mechanical properties (indentation modulus and hardness), composition (mineral-to-matrix ratio, carbonate substitution, and crystallinity), and aligned collagen content (aligned collagen peak height ratio) were sampled along three radial lines in three osteons per sample by nanoindentation, Raman spectroscopy, and second harmonic generation microscopy, respectively. Indentation modulus, hardness, mineral-to-matrix ratio, carbonate substitution, and aligned collagen peak height ratio followed biphasic relationships with animal age, increasing sharply during rapid growth before leveling off at sexual maturity. Mineral-to-matrix ratio and carbonate substitution increased 12% and 6.7%, respectively, per year across young animals during growth, corresponding with a nearly 7% increase in stiffness and hardness. Carbonate substitution and aligned collagen peak height ratio both increased with tissue age, increasing 6-12% across the osteon radii. Indentation modulus most strongly correlated with mineral-to-matrix ratio, which explained 78% of the variation in indentation modulus. Overall, the measured compositional and mechanical parameters were the lowest in tissue of the youngest animals. These results demonstrate that composition and mechanical function are closely related and influenced by tissue and animal age.

Contribution of mineral to bone structural behavior and tissue mechanical properties.

Bone geometry and tissue material properties jointly govern whole-bone structural behavior. While the role of geometry in structural behavior is well characterized, the contribution of the tissue material properties is less clear, partially due to the multiple tissue constituents and hierarchical levels at which these properties can be characterized. Our objective was to elucidate the contribution of the mineral phase to bone mechanical properties across multiple length scales, from the tissue material level to the structural level. Vitamin D and calcium deficiency in 6-week-old male rats was employed as a model of reduced mineral content with minimal collagen changes. The structural properties of the humeri were measured in three-point bending and related to the mineral content and geometry from microcomputed tomography. Whole-cortex and local bone tissue properties were examined with infrared (IR) spectroscopy, Raman spectroscopy, and nanoindentation to understand the role of altered mineral content on the constituent material behavior. Structural stiffness (-47%) and strength (-50%) were reduced in vitamin D-deficient (-D) humeri relative to controls. Moment of inertia (-38%), tissue mineral density (TMD, -9%), periosteal mineralization (-28%), and IR mineral:matrix ratio (-19%) were reduced in -D cortices. Thus, both decreased tissue mineral content and changes in cortical geometry contributed to impaired skeletal load-bearing function. In fact, 97% of the variability in humeral strength was explained by moment of inertia, TMD, and IR mineral:matrix ratio. The strong relationships between structural properties and cortical material composition demonstrate a critical role of the microscale material behavior in skeletal load-bearing performance.

Effects of tissue age on bone tissue material composition and nanomechanical properties in the rat cortex.

Although osteoporosis is known to alter bone tissue composition, the effects of such compositional changes on tissue material properties have not yet been examined. The natural gradient in tissue mineral content arising from skeletal appositional growth provides a basic model for investigation of relationships between tissue composition and mechanical properties. The purpose of this study was to examine the effects of tissue age on bone tissue composition and nanomechanical properties. The nanomechanical properties and composition of regions of differing tissue age were characterized in the femoral cortices of growing rats using nanoindentation and Raman spectroscopy. In addition, spatial maps of the properties of periosteal tissue were examined to investigate in detail the spatial gradients in the properties of newly formed tissue. Newly formed tissue (0-4 days) was 84% less stiff and had 79% lower mineral:matrix ratio than older intracortical (15-70 days) tissue. Tissue modulus, hardness, mineral:matrix ratio, and carbonate:phosphate ratio increased sharply with distance from the periosteum and attained the properties of intracortical tissue within 4 days of formation. The mineral: matrix ratio explained 54% and 62% of the variation in tissue indentation modulus and hardness, respectively. Our data demonstrate significant variations in tissue mechanical properties with tissue age and relate mechanical properties to composition at the microscale.

Effects of surface roughness and maximum load on the mechanical properties of cancellous bone measured by nanoindentation.

The effects of two key experimental parameters on the measured nanomechanical properties of lamellar and interlamellar tissue were examined in dehydrated rabbit cancellous bone. An anhydrous sample preparation protocol was developed to maintain surface integrity and produce RMS surface roughnesses approximately 10 nm (5x5-microm2 area). The effects of surface roughness and maximum nanoindentation load on the measured mechanical properties were examined in two samples of differing surface roughness using maximum loads ranging from 250 to 3000 microN. As the ratio of indentation depth to surface roughness decreased below approximately 3:1, the variability in material properties increased substantially. At low loads, the indentation modulus of the lamellar bone was approximately 20% greater than that of the interlamellar bone, while at high loads the measured properties of both layers converged to an intermediate value. Relatively shallow indentations made on smooth surfaces revealed significant differences in the properties of lamellar and interlamellar bone that support microstructural observations that lamellar bone is more mineralized than interlamellar bone.