Versatile Patterning of Liquid Metal via Multiphase 3D Printing.

This paper presents a scalable and straightforward technique for the immediate patterning of liquid metal/polymer composites via multiphase 3D printing. Capitalizing on the polymer's capacity to confine liquid metal (LM) into diverse patterns. The interplay between distinctive fluidic properties of liquid metal and its self-passivating oxide layer within an oxidative environment ensures a resilient interface with the polymer matrix. This study introduces an inventive approach for achieving versatile patterns in eutectic gallium indium (EGaIn), a gallium alloy. The efficacy of pattern formation hinges on nozzle's design and internal geometry, which govern multiphase interaction. The interplay between EGaIn and polymer within the nozzle channels, regulated by variables such as traverse speed and material flow pressure, leads to periodic patterns. These patterns, when encapsulated within a dielectric polymer polyvinyl alcohol (PVA), exhibit an augmented inherent capacitance in capacitor assemblies. This discovery not only unveils the potential for cost-effective and highly sensitive capacitive pressure sensors but also underscores prospective applications of these novel patterns in precise motion detection, including heart rate monitoring, and comprehensive analysis of gait profiles. The amalgamation of advanced materials and intricate patterning techniques presents a transformative prospect in the domains of wearable sensing and comprehensive human motion analysis.

Tooth acellular extrinsic fibre cementum incremental lines in humans are formed by parallel branched Sharpey's fibres and not by its mineral phase.

In humans, the growth pattern of the acellular extrinsic fibre cementum (AEFC) has been useful to estimate the age-at-death. However, the structural organization behind such a pattern remains poorly understood. In this study tooth cementum from seven individuals from a Mexican modern skeletal series were analyzed with the aim of unveiling the AEFC collagenous and mineral structure using multimodal imaging approaches. The organization of collagen fibres was first determined using: light microscopy, transmission electron microscopy (TEM), electron tomography, and plasma FIB scanning electron microscopy (PFIB-SEM) tomography. The mineral properties were then investigated using: synchrotron small-angle X-ray scattering (SAXS) for T-parameter (correlation length between mineral particles); synchrotron X-ray diffraction (XRD) for L-parameter (mineral crystalline domain size estimation), alignment parameter (crystals preferred orientation) and lattice parameters a and c; as well as synchrotron X-ray fluorescence for spatial distribution of calcium, phosphorus and zinc. Results show that Sharpey's fibres branched out fibres that cover and uncover other collagen bundles forming aligned arched structures that are joined by these same fibres but in a parallel fashion. The parallel fibres are not set as a continuum on the same plane and when they are superimposed project the AEFC incremental lines due to the collagen birefringence. The orientation of the apatite crystallites is subject to the arrangement of the collagen fibres, and the obtained parameter values along with the elemental distribution maps, revealed this mineral tissue as relatively homogeneous. Therefore, no intrinsic characteristics of the mineral phase could be associated with the alternating AEFC incremental pattern.

Characterization of PEDOT:PSS Nanofilms Printed via Electrically Assisted Direct Ink Deposition with Ultrasonic Vibrations.

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has emerged as a promising conductive polymer for constructing efficient hole-transport layers (HTLs) in perovskite solar cells (PSCs). However, conventional fabrication methods, such as spin coating, spray coating, and slot-die coating, have resulted in PEDOT:PSS nanofilms with limited performance, characterized by a low density and non-uniform nanostructures. We introduce a novel 3D-printing approach called electrically assisted direct ink deposition with ultrasonic vibrations (EF-DID-UV) to overcome these challenges. This innovative printing method combines programmable acoustic field modulation with electrohydrodynamic spraying, providing a powerful tool for controlling the PEDOT:PSS nanofilm's morphology precisely. The experimental findings indicate that when PEDOT:PSS nanofilms are crafted using horizontal ultrasonic vibrations, they demonstrate a uniform dispersion of PEDOT:PSS nanoparticles, setting them apart from instances involving vertical ultrasonic vibrations, both prior to and after the printing process. In particular, when horizontal ultrasonic vibrations are applied at a low amplitude (0.15 A) during printing, these nanofilms showcase exceptional wettability performance, with a contact angle of 16.24°, and impressive electrical conductivity of 2092 Ω/square. Given its ability to yield high-performance PEDOT:PSS nanofilms with precisely controlled nanostructures, this approach holds great promise for a wide range of nanotechnological applications, including the production of solar cells, wearable sensors, and actuators.

Subcanalicular Nanochannel Volume Is Inversely Correlated With Calcium Content in Human Cortical Bone.

The spatial distribution of mineralization density is an important signature of bone growth and remodeling processes, and its alterations are often related to disease. The extracellular matrix of some vertebrate mineralized tissues is known to be perfused by a lacunocanalicular network (LCN), a fluid-filled unmineralized structure that harbors osteocytes and their fine processes and transports extracellular fluid and its constituents. The current report provides evidence for structural and compositional heterogeneity at an even smaller, subcanalicular scale. The work reveals an extensive unmineralized three-dimensional (3D) network of nanochannels (~30 nm in diameter) penetrating the mineralized extracellular matrix of human femoral cortical bone and encompassing a greater volume fraction and surface area than these same parameters of the canaliculi comprising the LCN. The present study combines high-resolution focused ion beam-scanning electron microscopy (FIB-SEM) to investigate bone ultrastructure in 3D with quantitative backscattered electron imaging (qBEI) to estimate local bone mineral content. The presence of nanochannels has been found to impact qBEI measurements fundamentally, such that volume percentage (vol%) of nanochannels correlates inversely with weight percentage (wt%) of calcium. This mathematical relationship between nanochannel vol% and calcium wt% suggests that the nanochannels could potentially provide space for ion and small molecule transport throughout the bone matrix. Collectively, these data propose a reinterpretation of qBEI measurements, accounting for nanochannel presence in human bone tissue in addition to collagen and mineral. Further, the results yield insight into bone mineralization processes at the nanometer scale and present the possibility for a potential role of the nanochannel system in permitting ion and small molecule diffusion throughout the extracellular matrix. Such a possible function could thereby lead to the sequestration or occlusion of the ions and small molecules within the extracellular matrix. © 2022 The Authors. Journal of Bone and Mineral Research published by Wiley Periodicals LLC on behalf of American Society for Bone and Mineral Research (ASBMR).

Atom probe tomography for biomaterials and biomineralization.

Biominerals and biomaterials are part of our daily lives, from our skeleton and teeth to coral reefs and carbon-capturing single-cell organisms in the oceans, to engineered ceramics comprising our toothpaste and bone replacements. Many biominerals are hierarchically structured with remarkable material properties that arise from their unique combination of organic and inorganic components. Such structural hierarchy is often formed through a process of biomineralization. However, many fundamental questions remain regarding mineralization events in bones or teeth, and near biomaterials, partly due to the challenges in characterizing three-dimensional (3D) structure and chemical composition simultaneously at the nanometer scale. Atom probe tomography (APT) is a 3D characterization technique that combines both sub-nanometer spatial resolution and compositional sensitivity down to tens of parts per million. While APT is well-established in application to conventional engineering materials, recent years have seen its expansion into biomineralization research. Here, we focus our review on APT applications to biominerals, biomaterials and biointerfaces, providing a high-level summary of findings, as well as a primer on theory and best practices specific to the biomineralization community. We show that APT is a promising characterization tool, where its unique ability to quantify 3D chemical composition is not only complementary to other microscopy techniques but could become an integral part of biomaterial research. With the emerging trends of correlative and cryogenic workflow, notwithstanding the challenges outlined herein, APT has the potential to improve understanding of a broader range of biomaterials, while deriving innovative perspectives on clinical applications and strategies for biomaterial design. STATEMENT OF SIGNIFICANCE: Atom probe tomography (APT) is a three-dimensional characterization technique that can provide quantitative elemental and isotopic analysis with sub-nanometer resolution and compositional sensitivity down to tens of parts per million. These capabilities make it uniquely positioned for the analysis of biomineralized materials, both natural and synthetic. Here, we review the various applications of APT to the field of biomineralization, including applications in biominerals, biomaterials, biointerfaces and other biological materials, such as cells or proteins. A brief but comprehensive summary of the relevant technical concepts, limitations, and future perspectives to enable growth in this field are also included. Although APT is relatively new to the field of biomineralization, it has shown the potential to transform our basic understanding of biomineralization mechanisms and better inform biomaterials design.

Bone mineral organization at the mesoscale: A review of mineral ellipsoids in bone and at bone interfaces.

Much debate still revolves around bone architecture, especially at the nano- and microscale. Bone is a remarkable material where high strength and toughness coexist thanks to an optimized composition of mineral and protein and their hierarchical organization across several distinct length scales. At the nanoscale, mineralized collagen fibrils act as building block units. Despite their key role in biological and mechanical functions, the mechanisms of collagen mineralization and the precise arrangement of the organic and inorganic constituents in the fibrils remains not fully elucidated. Advances in three-dimensional (3D) characterization of mineralized bone tissue by focused ion beam-scanning electron microscopy (FIB-SEM) revealed mineral-rich regions geometrically approximated as prolate ellipsoids, much larger than single collagen fibrils. These structures have yet to become prominently recognized, studied, or adopted into biomechanical models of bone. However, they closely resemble the circular to elliptical features previously identified by scanning transmission electron microscopy (STEM) in two-dimensions (2D). Herein, we review the presence of mineral ellipsoids in bone as observed with electron-based imaging techniques in both 2D and 3D with particular focus on different species, anatomical locations, and in proximity to natural and synthetic biomaterial interfaces. This review reveals that mineral ellipsoids are a ubiquitous structure in all the bones and bone-implant interfaces analyzed. This largely overlooked hierarchical level is expected to bring different perspectives to our understanding of bone mineralization and mechanical properties, in turn shedding light on structure-function relationships in bone. STATEMENT OF SIGNIFICANCE: In bone, the hierarchical organization of organic (mainly collagen type I) and inorganic (calcium-phosphate mineral) components across several length scales contributes to a unique combination of strength and toughness. However, aspects related to the collagen-mineral organization and to mineralization mechanisms remain unclear. Here, we review the presence of mineral prolate ellipsoids across a variety of species, anatomical locations, and interfaces, both natural and with synthetic biomaterials. These mineral ellipsoids represent a largely unstudied feature in the organization of bone at the mesoscale, i.e., at a level connecting nano- and microscale. Thorough understanding of their origin, development, and structure can provide valuable insights into bone architecture and mineralization, assisting the treatment of bone diseases and the design of bio-inspired materials.

Breast cancer-secreted factors perturb murine bone growth in regions prone to metastasis.

Breast cancer frequently metastasizes to bone, causing osteolytic lesions. However, how factors secreted by primary tumors affect the bone microenvironment before the osteolytic phase of metastatic tumor growth remains unclear. Understanding these changes is critical as they may regulate metastatic dissemination and progression. To mimic premetastatic bone adaptation, immunocompromised mice were injected with MDA-MB-231-conditioned medium [tumor-conditioned media (TCM)]. Subsequently, the bones of these mice were subjected to multiscale, correlative analysis including RNA sequencing, histology, micro-computed tomography, x-ray scattering analysis, and Raman imaging. In contrast to overt metastasis causing osteolysis, TCM treatment induced new bone formation that was characterized by increased mineral apposition rate relative to control bones, altered bone quality with less matrix and more carbonate substitution, and the deposition of disoriented mineral near the growth plate. Our study suggests that breast cancer-secreted factors may promote perturbed bone growth before metastasis, which could affect initial seeding of tumor cells.

Globular structure of the hypermineralized tissue in human femoral neck.

Bone becomes more fragile with ageing. Among many structural changes, a thin layer of highly mineralized and brittle tissue covers part of the external surface of the thin femoral neck cortex in older people and has been proposed to increase hip fragility. However, there have been very limited reports on this hypermineralized tissue in the femoral neck, especially on its ultrastructure. Such information is critical to understanding both the mineralization process and its contributions to hip fracture. Here, we use multiple advanced techniques to characterize the ultrastructure of the hypermineralized tissue in the neck across various length scales. Synchrotron radiation micro-CT found larger but less densely distributed cellular lacunae in hypermineralized tissue than in lamellar bone. When examined under FIB-SEM, the hypermineralized tissue was mainly composed of mineral globules with sizes varying from submicron to a few microns. Nano-sized channels were present within the mineral globules and oriented with the surrounding organic matrix. Transmission electron microscopy showed the apatite inside globules were poorly crystalline, while those at the boundaries between the globules had well-defined lattice structure with crystallinity similar to the apatite mineral in lamellar bone. No preferred mineral orientation was observed both inside each globule and at the boundaries. Collectively, we conclude based on these new observations that the hypermineralized tissue is non-lamellar and has less organized mineral, which may contribute to the high brittleness of the tissue.

Three-dimensional structural interrelations between cells, extracellular matrix, and mineral in normally mineralizing avian leg tendon.

The spatial-temporal relationship between cells, extracellular matrices, and mineral deposits is fundamental for an improved understanding of mineralization mechanisms in vertebrate tissues. By utilizing focused ion beam-scanning electron microscopy with serial surface imaging, normally mineralizing avian tendons have been studied with nanometer resolution in three dimensions with volumes exceeding tens of micrometers in range. These parameters are necessary to yield sufficiently fine ultrastructural details while providing a comprehensive overview of the interrelationships between the tissue structural constituents. Investigation reveals a complex lacuno-canalicular network in highly mineralized tendon regions, where ∼100 nm diameter canaliculi emanating from cell (tenocyte) lacunae surround extracellular collagen fibril bundles. Canaliculi are linked to smaller channels of ∼40 nm diameter, occupying spaces between fibrils. Close to the tendon mineralization front, calcium-rich deposits appear between the fibrils and, with time, mineral propagates along and within them. These close associations between tenocytes, tenocyte lacunae, canaliculi, small channels, collagen, and mineral suggest a concept for the mineralization process, where ions and/or mineral precursors may be transported through spaces between fibrils before they crystallize along the surface of and within the fibrils.

Hypermineralization in the femoral neck of the elderly.

Hip fragility depends on the decline in bone mass as well as changes in bone microstructure and the properties of bone mineral and organic matrix. Although it is well-established that low bone mass or osteoporosis is a key factor in hip fracture risk, it is striking to observe that 92% of 24 patients who have sustained an intracapsular hip fracture showed hypermineralization at the superior-anterior quadrant, a critical region associated with increased hip fracture risk. In-depth material studies on a total of 12 human cadaver femurs revealed increased degree of mineralization in the hypermineralized tissue: calcium weight percentage as measured by quantitative backscattered electron imaging increased by approximately 15% compared with lamellar bone; mineral-to-matrix ratio obtained by Raman microspectroscopy imaging also increased. Immunohistochemistry revealed localized type II collagen in the hypermineralized region, implying its cartilaginous nature. At the ultrastructural level, X-ray scattering revealed significantly smaller (on average 2.3 nm thick and 15.6 nm long) and less ordered bone minerals in the hypermineralized tissue. Finally, the hypermineralized tissue was more brittle than lamellar bone under hydrated state - cracks propagated easily in the hypermineralized region but stopped at the lamellar boundary. This study demonstrates that hypermineralization of femoral neck cortical bone is a source of bone fragility which is worth considering in future fracture risk assessment when the origin of hip fracture is unclear based on current evaluation standards. STATEMENT OF SIGNIFICANCE: Hypermineralization of femoral cortical bone in older adults might occur in many more hip fracture cases than presently known. Yet, this tissue remains largely unknown to the orthopedic community possibly due to coarse resolution of clinical imaging. The current study showed the hypermineralized tissue had reduced fracture resistance which could be attributed to the material changes in mineral content, organic matrix, and mineral platelets properties. It thus could be a source for fracture initiation. Consequently, we believe hypermineralization of femoral neck cortical bone should be considered in hip fragility assessment, especially when low bone mass cannot be identified as a primary contributor to hip fracture.

Clinical hip fracture is accompanied by compression induced failure in the superior cortex of the femoral neck.

Hip fractures pose a major health problem throughout the world due to their devastating impact. Current theories for why these injuries are so prevalent in the elderly point to an increased propensity to fall and decreases in bone mass with ageing. However, the fracture mechanisms, particularly the stress and strain conditions leading to bone failure at the hip remain unclear. Here, we directly examined the cortical bone from clinical intra-capsular hip fractures at a microscopic level, and found strong evidence of compression induced failure in the superior cortex. A total of 143 sections obtained from 24 femoral neck samples that were retrieved from 24 fracturing patients at surgery were examined using laser scanning confocal microscopy (LSCM) after fluorescein staining. The stained microcracks showed significantly higher density in the superior cortex than in the inferior cortex, indicating a greater magnitude of strain in the superior femoral neck during the failure-associated deformation and fracture process. The predominant stress state for each section was reconstructed based on the unique correlation between the microcrack pattern and the stress state. Specifically, we found clear evidence of longitudinal compression and buckling as the primary failure mechanisms in the superior cortex. These findings demonstrate the importance of microcrack analysis in studying clinical hip fractures, and point to the central role of the superior cortex failure as an important aspect of the failure initiation in clinical intra-capsular hip fractures.

Role of Creativity in the Effectiveness of Cognitive Reappraisal.

As a well-recognized and widely adopted emotional regulation strategy, cognitive reappraisal has generally been proven to be efficient. However, the cognitive mechanism underlying regulatory efficiency, particularly the role of creativity, in cognitive reappraisal is unclear. Although previous studies have evaluated the relationship between creativity and reappraisal from the perspectives of generation (i.e., generating cognitive reappraisals and generating creative ideas involve similar cognitive neural networks) and individual differences (i.e., the ability to generate different cognitive reappraisals can be predicted by scores on creativity-related tests), how cognitive reappraisal's efficiency can be related to creativity is still unknown. In this research, we assessed the relationship between cognitive reappraisal's creativity and its effectiveness in regulating negative emotion. In Study 1, participants were asked to generate reappraisals of negative stimuli and then evaluate the creativity and regulatory effectiveness of these reappraisals. The results indicated positive correlation between creativity rating and regulatory effectiveness, but we found that it was difficult for the participants to generate highly creative reappraisals on their own. Therefore, in Study 2, we showed participants well-prepared reappraisal materials that varied in their creativity and asked them to evaluate their regulatory effectiveness and creativity. The results suggested that creativity and appropriateness were significant predictors of the regulating effects of the reappraisal and that creativity was the most dominant predictor. In summary, both experiments found a positive correlation between reappraisal's creativity and effectiveness, thus implying that creativity plays an important role in reappraisal.

Shear deformation and fracture of human cortical bone.

Bone can be viewed as a nano-fibrous composite with complex hierarchical structures. Its deformation and fracture behaviors depend on both the local structure and the type of stress applied. In contrast to the extensive studies on bone fracture under compression and tension, there is a lack of knowledge on the fracture process under shear, a stress state often exists in hip fracture. This study investigated the mechanical behavior of human cortical bone under shear, with the focus on the relation between the fracture pattern and the microstructure. Iosipescu shear tests were performed on notched rectangular bar specimens made from human cortical bone. They were prepared at different angles (i.e. 0°, 30°, 60° and 90°) with respect to the long axis of the femoral shaft. The results showed that human cortical bone behaved as an anisotropic material under shear with the highest shear strength (~50MPa) obtained when shearing perpendicular to the Haversian systems or secondary osteons. Digital image correlation (DIC) analysis found that shear strain concentration bands had a close association with long bone axis with an average deviation of 11.8° to 18.5°. The fracture pattern was also greatly affected by the structure with the crack path generally following the direction of the long axes of osteons. More importantly, we observed unique peripheral arc-shaped microcracks within osteons, using laser scanning confocal microscopy (LSCM). They were generally long cracks that developed within a lamella without crossing the boundaries. This microcracking pattern clearly differed from that created under either compressive or tensile stress: these arc-shaped microcracks tended to be located away from the Haversian canals in early-stage damaged osteons, with ~70% developing in the outer third osteonal wall. Further study by second harmonic generation (SHG) and two-photon excitation fluorescence (TPEF) microscopy revealed a strong influence of the organization of collagen fibrils on shear microcracking. This study concluded that shear-induced microcracking of human cortical bone follows a unique pattern that is governed by the lamellar structure of the osteons.

Processing-structure-property relationships of Bi2WO6 nanostructures as visible-light-driven photocatalyst.

QDS modified Bi(2)WO(6) (BWO) nanostructures were processed by calcination at different temperatures. A strong correlation was found among the processing, structure and properties of the samples. With increasing calcination temperature from 200°C to 500°C, the crystallinity increased and the BWO QDS gradually disappeared from the nanostructures. Both surface area and band gap of the samples decreased. The light absorption of the samples became lower for the long-wavelength range, accompanied by a red shift of the absorption edge. The photocatalytic activity of the samples decreased after calcination at higher temperature. The competitive relations between crystallinity and surface area in affecting photocatalytic activity were discussed. The role of BWO QDS that played in enhancement of photocatalytic activity was also revealed by studying structure and property evolution of the calcined samples.