Biofilms are multicellular microbial communities that encase themselves in an extracellular matri... more Biofilms are multicellular microbial communities that encase themselves in an extracellular matrix (ECM) of secreted biopolymers and attach to surfaces and interfaces. Bacterial biofilms are detrimental in hospital and industrial settings, but they can be beneficial in agricultural contexts. An essential property of biofilms that grants them with increased survival relative to planktonic cells is phenotypic heterogeneity; the division of the biofilm population into functionally distinct subgroups of cells. Phenotypic heterogeneity in biofilms can be traced to the cellular level, however, the molecular structures and elemental distribution across whole biofilms as well as possible linkages between them remain unexplored. Mapping X-ray diffraction (XRD) across intact biofilms in time and space, we revealed the dominant structural features in Bacillus subtilis biofilms, stemming from matrix components, spores and water. By simultaneously following the X-ray fluorescence (XRF) signal of...
We identify the presence of multiple vascular channels within the spider fang. These channels see... more We identify the presence of multiple vascular channels within the spider fang. These channels seem to serve the transport of zinc to the tip of the fang to cross-link the protein matrix by binding to histidine residues. According to amino acid and elemental analysis of fangs extracted shortly after ecdysis His-rich proteins are deposited before Zn is incorporated into the cuticle. Microscopic and spectroscopic investigations in the electron microscope and synchrotron radiation experiments suggest that Zn ions are transported through these channels in a liable (yet unidentified) form, and then form stable complexes upon His binding. The resulting cross-linking through the Zn-His complexes is conferring hardness to the fang. Our observations of nano-channels serving the Zn-transport within the His-rich protein matrix of the fiber reinforced spider fang may also support recent bio-inspired attempts to design artificial polymeric vascular materials for self-healing and in-situ curing.
Highly sensitive lyriform organs located on the legs of the wandering spider Cupiennius salei all... more Highly sensitive lyriform organs located on the legs of the wandering spider Cupiennius salei allow the spider to detect nanometer-scale strains in the exoskeleton resulting from locomotion or substrate vibrations. Morphological features of the lyriform organs result in their specialization and selective sensitivity to specific mechanical stimuli, which make them interesting for bioinspired strain sensors. Here we utilize atomic force microscopy (AFM)-based force spectroscopy to probe nano-scale mechanical properties of the covering membrane of two lyriform organs found on Cupiennius salei: the vibration sensitive metatarsal lyriform organ (HS10) and the proprioreceptive tibial lyriform organ (HS8). Force distance curves (FDCs) obtained from AFM measurements displayed characteristic multi-layer structure behavior, with calculated elastic moduli ranging from 150 MPa to 500 MPa for different regions and indentation depths. In addition, we probed the lyriform organs with a large radius...
X-ray absorption near-edge structure (XANES) spectroscopy and spectromicroscopy have been extensi... more X-ray absorption near-edge structure (XANES) spectroscopy and spectromicroscopy have been extensively used to characterize biominerals. Using either Ca or C spectra, unique information has been obtained regarding amorphous biominerals and nanocrystal orientations. Building on these results, we demonstrate that recording XANES spectra of calcium carbonate at the oxygen K-edge enables polarization-dependent imaging contrast (PIC) mapping with unprecedented contrast, signal-to-noise ratio, and magnification. O and Ca spectra are presented for six calcium carbonate minerals: aragonite, calcite, vaterite, monohydrocalcite, and both hydrated and anhydrous amorphous calcium carbonate. The crystalline minerals reveal excellent agreement of the extent and direction of polarization dependences in simulated and experimental XANES spectra due to X-ray linear dichroism. This effect is particularly strong for aragonite, calcite, and vaterite. In natural biominerals, oxygen PIC-mapping generated high-magnification maps of unprecedented clarity from nacre and prismatic structures and their interface in Mytilus californianus shells. These maps revealed blocky aragonite crystals at the nacre-prismatic boundary and the narrowest calcite needle-prisms. In the tunic spicules of Herdmania momus, O PIC-mapping revealed the size and arrangement of some of the largest vaterite single crystals known. O spectroscopy therefore enables the simultaneous measurement of chemical and orientational information in CaCO3 biominerals and is thus a powerful means for analyzing these and other complex materials. As described here, PIC-mapping and spectroscopy at the O K-edge are methods for gathering valuable data that can be carried out using spectromicroscopy beamlines at most synchrotrons without the expense of additional equipment.
Coccoliths are calcitic particles produced inside the cells of unicellular marine algae known as ... more Coccoliths are calcitic particles produced inside the cells of unicellular marine algae known as coccolithophores. They are abundant components of sea-floor carbonates, and the stoichiometry of calcium to other elements in fossil coccoliths is widely used to infer past environmental conditions. Here we study cryo-preserved cells of the dominant coccolithophore Emiliania huxleyi using state-of-the-art nanoscale imaging and spectroscopy. We identify a compartment, distinct from the coccolith-producing compartment, filled with high concentrations of a disordered form of calcium. Co-localized with calcium are high concentrations of phosphorus and minor concentrations of other cations. The amounts of calcium stored in this reservoir seem to be dynamic and at a certain stage the compartment is in direct contact with the coccolith-producing vesicle, suggesting an active role in coccolith formation. Our findings provide insights into calcium accumulation in this important calcifying organism.
Marine mussels tether to seashore surfaces with byssal threads, proteinaceous fibers that effecti... more Marine mussels tether to seashore surfaces with byssal threads, proteinaceous fibers that effectively dissipate energy from crashing waves. Protein-metal coordination bonds have been proposed to contribute to the characteristic mechanical and self-healing properties of byssal threads; however, very little is understood about how these cross-links function at the molecular level. In the present study, combined Raman and X-ray absorption spectroscopy (XAS) measurements were employed to confirm the presence of protein-Zn(2+) coordination bonds in the mussel byssus and to monitor transitions in the coordination structure during thread deformation and self-healing. Results indicate that Zn(2+) coordination bonds, primarily mediated via histidine, are ruptured during thread yield and reformed immediately following thread relaxation. Mechanical healing, on the other hand, is correlated with the transition toward shorter coordination bond lengths. Calculation of the healing activation energy suggests that protein-Zn bond exchange provides a primary rate-limiting step during healing.
Synchrotron X-ray diffraction was applied to study the structure of biogenic α-chitin crystals co... more Synchrotron X-ray diffraction was applied to study the structure of biogenic α-chitin crystals composing the tendon of the spider Cupiennius salei. Measurements were carried out on pristine chitin crystals stabilized by proteins and water, as well as after their deproteinization and dehydration. We found substantial shifts (up to Δq/q=9% in the wave vector in q-space) in the (020) diffraction peak position between intact and purified chitin samples. However, chitin lattice parameters extracted from the set of reflections (hkl), which did not contain the (020)-reflection, showed no systematic variation between the pristine and the processed samples. The observed shifts in the (020) peak position are discussed in terms of the ordering-induced modulation of the protein and water electron density near the surface of the ultra-thin chitin fibrils due to strong protein/chitin and water/chitin interactions. The extracted modulation periods can be used as a quantitative parameter characterizing the interaction length.
A generic character of the genus Spiophanes (Annelida, Sedentaria: Spionidae) is the presence of ... more A generic character of the genus Spiophanes (Annelida, Sedentaria: Spionidae) is the presence of parapodial glandular organs. Parapodial glandular organs in Spiophanes species include secretory cells with cup-shaped microvilli, similar to those present in deep-sea inhabiting vestimentiferans and frenulate Siboglinidae. These cells are supposed to secrete β-chitin for tube-building. In this study, transverse histological and/or ultrathin sections of parapodial glandular organs and tubes of Spiophanes spp. as well as of Glandulospio orestes (Spionidae) and Owenia fusiformis (Oweniidae) were examined. Fluorescent markers together with confocal laser scanning microscopy, and Raman spectroscopy were used to detect chitin in the parapodial glandular organs of Spiophanes and/or in the glands of Owenia and Glandulospio. Tubes of these taxa were tested for chitin to elucidate the use of it for tube-building. The examinations revealed a distinct labelling of the gland contents. Raman spectros...
ABSTRACT Calcium carbonate is a common constituent of many natural materials, such as shells and ... more ABSTRACT Calcium carbonate is a common constituent of many natural materials, such as shells and skeletons of marine animals. While it is well documented that additives (organic and inorganic) modulate the crystallization of amorphous calcium carbonate (ACC), the effects of the intrinsic physicochemical characteristics of ACC such as particle size, shape and water content on the transformation to crystalline polymorphs are still poorly understood. Here we investigated the effect of particle size by preparing ACC nanoparticles with an average size ranging from ~66 nm to ~196 nm using a high-resolution titration setup. Our results show that the particle size determined the polymorph selection in solution; an increasing proportion of vaterite to calcite was observed with decreasing particle size. The polymorph selection was ascribed to a higher apparent solubility of ACC with decreasing particle size, a parameter from which we could determine the surface energy of ACC to be ~0.33 J/m2. Upon heating, particle size showed the opposite effect, as smaller particles favored a higher crystallization temperature from ACC into (only) calcite. When the particle size was large enough, crystallization occurred concomitantly with the removal of bulk water at lower temperatures, where the smallest particles transformed at ~310 °C, only after losing the final (surface) water. Our results highlight the importance of particle size as well as the crystallization conditions on the stability and transformation mechanisms of ACC.
A strain-sensing lyriform organ (HS-10) found on all of the legs of a Central American wandering ... more A strain-sensing lyriform organ (HS-10) found on all of the legs of a Central American wandering spider (Cupiennius salei) detects courtship, prey and predator vibrations transmitted by the plant on which it sits. It has been suggested that the viscoelastic properties of a cuticular pad directly adjacent to the sensory organ contribute to the organ's pronounced high-pass characteristics. Here, we investigate the micromechanical properties of the cuticular pad biomaterial in search of a deeper understanding of its impact on the function of the vibration sensor. These properties are considered to be an effective adaptation for the selective detection of signals for frequencies >40 Hz. Using surface force spectroscopy mapping we determine the elastic modulus of the pad surface over a temperature range of 15-40 °C at various loading frequencies. In the glassy state, the elastic modulus was ~100 MPa, while in the rubbery state the elastic modulus decreased to 20 MPa. These data ar...
Protein-metal interactions--traditionally regarded for roles in metabolic processes--are now know... more Protein-metal interactions--traditionally regarded for roles in metabolic processes--are now known to enhance the performance of certain biogenic materials, influencing properties such as hardness, toughness, adhesion, and self-healing. Design principles elucidated through thorough study of such materials are yielding vital insights for the design of biomimetic metallopolymers with industrial and biomedical applications. Recent advances in the understanding of the biological structure-function relationships are highlighted here with a specific focus on materials such as arthropod biting parts, mussel byssal threads, and sandcastle worm cement.
ABSTRACT Protein-Metall-Wechselwirkungen wurden bisher vor allem hinsichtlich ihrer Bedeutung in ... more ABSTRACT Protein-Metall-Wechselwirkungen wurden bisher vor allem hinsichtlich ihrer Bedeutung in Stoffwechselprozessen betrachtet. Aktuelle Forschungsergebnisse zeigen, dass sie auch die mechanischen Eigenschaften von Biomaterialien verbessern können, wie z. B. Härte, Zähigkeit, Haftung und die Fähigkeit zur Selbstheilung. Die zugrundeliegenden Prinzipien werden hier anhand einiger Beispiele, wie der Beißwerkzeuge von Arthropoden, der Byssusfäden von Miesmuscheln und des Zements von Sandburg-Würmern, besprochen. Diese neuen Erkenntnisse können auch für die Entwicklung von bio-inspirierten Metallopolymeren mit potentiellen Anwendungen in der Industrie und Biomedizin von Bedeutung sein.
ABSTRACT We apply advanced X-ray diffraction techniques at synchrotron microfocus beamlines in or... more ABSTRACT We apply advanced X-ray diffraction techniques at synchrotron microfocus beamlines in order to study the local ultrastructure of biogenic calcite with high spatial and angular resolution. Specifically, we investigate individual calcitic prisms extracted from Pinna nobilis mollusk shells with an aim to shed additional light on the structural aspects of organic/inorganic interfaces. We use annealing at elevated temperatures to destroy intracrystalline organics and measure the same prisms before and after annealing to achieve deeper understanding of the internal organization of these nanobiocomposites. Complementary nanoindentation measurements (also performed before and after annealing) allow us to elucidate the role of intracrystalline organics in increased hardness in pristine prisms and hardness reduction after annealing. We found that removal of intracrystalline organics during annealing facilitates generation of well-oriented lattice defects, which reduce the (006) diffraction intensity and are responsible for the [001]-elongated diffuse streaks nearby diffraction spots. These findings indicate the formation of internal materials discontinuities with smooth and flat interfaces. Such nanodiscontinuities facilitate microcrack propagation under load that explains the reduced hardness of calcitic prisms after annealing.
Journal of the Royal Society, Interface / the Royal Society, Jan 6, 2015
The metatarsal lyriform organ of the Central American wandering spider Cupiennius salei is its mo... more The metatarsal lyriform organ of the Central American wandering spider Cupiennius salei is its most sensitive vibration detector. It is able to sense a wide range of vibration stimuli over four orders of magnitude in frequency between at least as low as 0.1 Hz and several kilohertz. Transmission of the vibrations to the slit organ is controlled by a cuticular pad in front of it. While the mechanism of high-frequency stimulus transfer (above ca 40 Hz) is well understood and related to the viscoelastic properties of the pad's epicuticle, it is not yet clear how low-frequency stimuli (less than 40 Hz) are transmitted. Here, we study how the pad material affects the pad's mechanical properties and thus its role in the transfer of the stimulus, using a variety of experimental techniques, such as X-ray micro-computed tomography for three-dimensional imaging, X-ray scattering for structural analysis, and atomic force microscopy and scanning electron microscopy for surface imaging. ...
X-ray absorption near-edge structure (XANES) spectroscopy and spectromicroscopy have been extensi... more X-ray absorption near-edge structure (XANES) spectroscopy and spectromicroscopy have been extensively used to characterize biominerals. Using either Ca or C spectra, unique information has been obtained regarding amorphous biominerals and nanocrystal orientations. Building on these results, we demonstrate that recording XANES spectra of calcium carbonate at the oxygen K-edge enables polarization-dependent imaging contrast (PIC) mapping with unprecedented contrast, signal-to-noise ratio, and magnification. O and Ca spectra are presented for six calcium carbonate minerals: aragonite, calcite, vaterite, monohydrocalcite, and both hydrated and anhydrous amorphous calcium carbonate. The crystalline minerals reveal excellent agreement of the extent and direction of polarization dependences in simulated and experimental XANES spectra due to X-ray linear dichroism. This effect is particularly strong for aragonite, calcite, and vaterite. In natural biominerals, oxygen PIC-mapping generated high-magnification maps of unprecedented clarity from nacre and prismatic structures and their interface in Mytilus californianus shells. These maps revealed blocky aragonite crystals at the nacre-prismatic boundary and the narrowest calcite needle-prisms. In the tunic spicules of Herdmania momus, O PIC-mapping revealed the size and arrangement of some of the largest vaterite single crystals known. O spectroscopy therefore enables the simultaneous measurement of chemical and orientational information in CaCO3 biominerals and is thus a powerful means for analyzing these and other complex materials. As described here, PIC-mapping and spectroscopy at the O K-edge are methods for gathering valuable data that can be carried out using spectromicroscopy beamlines at most synchrotrons without the expense of additional equipment.
Most biological materials are nanocomposites characterized by a multi-level structural hierarchy.... more Most biological materials are nanocomposites characterized by a multi-level structural hierarchy. Particularly, the arthropod cuticle is a chitin-based composite material where the mechanical properties strongly depend on both molecular chitin/protein properties, and the structural arrangement of chitin-fibrils within the protein matrix. Here materials properties and structural organization of two types of cuticle from distantly related arthropods, the wandering spider Cupiennius salei and American lobster Homarus americanus were studied using nanoindentation and X-ray diffraction. The structural analysis of the two types of cuticle including the packing and alignment of chitin-fibrils is supported by Monte Carlo simulations of the experimental X-ray data, thereby regions of parallel and rotated fibril arrangement can be clearly distinguished. The tip of the spider fang which is used to inject venom into the prey was found to be considerably harder than the lobster carapace, while its stiffness is slightly lower.
Biofilms are multicellular microbial communities that encase themselves in an extracellular matri... more Biofilms are multicellular microbial communities that encase themselves in an extracellular matrix (ECM) of secreted biopolymers and attach to surfaces and interfaces. Bacterial biofilms are detrimental in hospital and industrial settings, but they can be beneficial in agricultural contexts. An essential property of biofilms that grants them with increased survival relative to planktonic cells is phenotypic heterogeneity; the division of the biofilm population into functionally distinct subgroups of cells. Phenotypic heterogeneity in biofilms can be traced to the cellular level, however, the molecular structures and elemental distribution across whole biofilms as well as possible linkages between them remain unexplored. Mapping X-ray diffraction (XRD) across intact biofilms in time and space, we revealed the dominant structural features in Bacillus subtilis biofilms, stemming from matrix components, spores and water. By simultaneously following the X-ray fluorescence (XRF) signal of...
We identify the presence of multiple vascular channels within the spider fang. These channels see... more We identify the presence of multiple vascular channels within the spider fang. These channels seem to serve the transport of zinc to the tip of the fang to cross-link the protein matrix by binding to histidine residues. According to amino acid and elemental analysis of fangs extracted shortly after ecdysis His-rich proteins are deposited before Zn is incorporated into the cuticle. Microscopic and spectroscopic investigations in the electron microscope and synchrotron radiation experiments suggest that Zn ions are transported through these channels in a liable (yet unidentified) form, and then form stable complexes upon His binding. The resulting cross-linking through the Zn-His complexes is conferring hardness to the fang. Our observations of nano-channels serving the Zn-transport within the His-rich protein matrix of the fiber reinforced spider fang may also support recent bio-inspired attempts to design artificial polymeric vascular materials for self-healing and in-situ curing.
Highly sensitive lyriform organs located on the legs of the wandering spider Cupiennius salei all... more Highly sensitive lyriform organs located on the legs of the wandering spider Cupiennius salei allow the spider to detect nanometer-scale strains in the exoskeleton resulting from locomotion or substrate vibrations. Morphological features of the lyriform organs result in their specialization and selective sensitivity to specific mechanical stimuli, which make them interesting for bioinspired strain sensors. Here we utilize atomic force microscopy (AFM)-based force spectroscopy to probe nano-scale mechanical properties of the covering membrane of two lyriform organs found on Cupiennius salei: the vibration sensitive metatarsal lyriform organ (HS10) and the proprioreceptive tibial lyriform organ (HS8). Force distance curves (FDCs) obtained from AFM measurements displayed characteristic multi-layer structure behavior, with calculated elastic moduli ranging from 150 MPa to 500 MPa for different regions and indentation depths. In addition, we probed the lyriform organs with a large radius...
X-ray absorption near-edge structure (XANES) spectroscopy and spectromicroscopy have been extensi... more X-ray absorption near-edge structure (XANES) spectroscopy and spectromicroscopy have been extensively used to characterize biominerals. Using either Ca or C spectra, unique information has been obtained regarding amorphous biominerals and nanocrystal orientations. Building on these results, we demonstrate that recording XANES spectra of calcium carbonate at the oxygen K-edge enables polarization-dependent imaging contrast (PIC) mapping with unprecedented contrast, signal-to-noise ratio, and magnification. O and Ca spectra are presented for six calcium carbonate minerals: aragonite, calcite, vaterite, monohydrocalcite, and both hydrated and anhydrous amorphous calcium carbonate. The crystalline minerals reveal excellent agreement of the extent and direction of polarization dependences in simulated and experimental XANES spectra due to X-ray linear dichroism. This effect is particularly strong for aragonite, calcite, and vaterite. In natural biominerals, oxygen PIC-mapping generated high-magnification maps of unprecedented clarity from nacre and prismatic structures and their interface in Mytilus californianus shells. These maps revealed blocky aragonite crystals at the nacre-prismatic boundary and the narrowest calcite needle-prisms. In the tunic spicules of Herdmania momus, O PIC-mapping revealed the size and arrangement of some of the largest vaterite single crystals known. O spectroscopy therefore enables the simultaneous measurement of chemical and orientational information in CaCO3 biominerals and is thus a powerful means for analyzing these and other complex materials. As described here, PIC-mapping and spectroscopy at the O K-edge are methods for gathering valuable data that can be carried out using spectromicroscopy beamlines at most synchrotrons without the expense of additional equipment.
Coccoliths are calcitic particles produced inside the cells of unicellular marine algae known as ... more Coccoliths are calcitic particles produced inside the cells of unicellular marine algae known as coccolithophores. They are abundant components of sea-floor carbonates, and the stoichiometry of calcium to other elements in fossil coccoliths is widely used to infer past environmental conditions. Here we study cryo-preserved cells of the dominant coccolithophore Emiliania huxleyi using state-of-the-art nanoscale imaging and spectroscopy. We identify a compartment, distinct from the coccolith-producing compartment, filled with high concentrations of a disordered form of calcium. Co-localized with calcium are high concentrations of phosphorus and minor concentrations of other cations. The amounts of calcium stored in this reservoir seem to be dynamic and at a certain stage the compartment is in direct contact with the coccolith-producing vesicle, suggesting an active role in coccolith formation. Our findings provide insights into calcium accumulation in this important calcifying organism.
Marine mussels tether to seashore surfaces with byssal threads, proteinaceous fibers that effecti... more Marine mussels tether to seashore surfaces with byssal threads, proteinaceous fibers that effectively dissipate energy from crashing waves. Protein-metal coordination bonds have been proposed to contribute to the characteristic mechanical and self-healing properties of byssal threads; however, very little is understood about how these cross-links function at the molecular level. In the present study, combined Raman and X-ray absorption spectroscopy (XAS) measurements were employed to confirm the presence of protein-Zn(2+) coordination bonds in the mussel byssus and to monitor transitions in the coordination structure during thread deformation and self-healing. Results indicate that Zn(2+) coordination bonds, primarily mediated via histidine, are ruptured during thread yield and reformed immediately following thread relaxation. Mechanical healing, on the other hand, is correlated with the transition toward shorter coordination bond lengths. Calculation of the healing activation energy suggests that protein-Zn bond exchange provides a primary rate-limiting step during healing.
Synchrotron X-ray diffraction was applied to study the structure of biogenic α-chitin crystals co... more Synchrotron X-ray diffraction was applied to study the structure of biogenic α-chitin crystals composing the tendon of the spider Cupiennius salei. Measurements were carried out on pristine chitin crystals stabilized by proteins and water, as well as after their deproteinization and dehydration. We found substantial shifts (up to Δq/q=9% in the wave vector in q-space) in the (020) diffraction peak position between intact and purified chitin samples. However, chitin lattice parameters extracted from the set of reflections (hkl), which did not contain the (020)-reflection, showed no systematic variation between the pristine and the processed samples. The observed shifts in the (020) peak position are discussed in terms of the ordering-induced modulation of the protein and water electron density near the surface of the ultra-thin chitin fibrils due to strong protein/chitin and water/chitin interactions. The extracted modulation periods can be used as a quantitative parameter characterizing the interaction length.
A generic character of the genus Spiophanes (Annelida, Sedentaria: Spionidae) is the presence of ... more A generic character of the genus Spiophanes (Annelida, Sedentaria: Spionidae) is the presence of parapodial glandular organs. Parapodial glandular organs in Spiophanes species include secretory cells with cup-shaped microvilli, similar to those present in deep-sea inhabiting vestimentiferans and frenulate Siboglinidae. These cells are supposed to secrete β-chitin for tube-building. In this study, transverse histological and/or ultrathin sections of parapodial glandular organs and tubes of Spiophanes spp. as well as of Glandulospio orestes (Spionidae) and Owenia fusiformis (Oweniidae) were examined. Fluorescent markers together with confocal laser scanning microscopy, and Raman spectroscopy were used to detect chitin in the parapodial glandular organs of Spiophanes and/or in the glands of Owenia and Glandulospio. Tubes of these taxa were tested for chitin to elucidate the use of it for tube-building. The examinations revealed a distinct labelling of the gland contents. Raman spectros...
ABSTRACT Calcium carbonate is a common constituent of many natural materials, such as shells and ... more ABSTRACT Calcium carbonate is a common constituent of many natural materials, such as shells and skeletons of marine animals. While it is well documented that additives (organic and inorganic) modulate the crystallization of amorphous calcium carbonate (ACC), the effects of the intrinsic physicochemical characteristics of ACC such as particle size, shape and water content on the transformation to crystalline polymorphs are still poorly understood. Here we investigated the effect of particle size by preparing ACC nanoparticles with an average size ranging from ~66 nm to ~196 nm using a high-resolution titration setup. Our results show that the particle size determined the polymorph selection in solution; an increasing proportion of vaterite to calcite was observed with decreasing particle size. The polymorph selection was ascribed to a higher apparent solubility of ACC with decreasing particle size, a parameter from which we could determine the surface energy of ACC to be ~0.33 J/m2. Upon heating, particle size showed the opposite effect, as smaller particles favored a higher crystallization temperature from ACC into (only) calcite. When the particle size was large enough, crystallization occurred concomitantly with the removal of bulk water at lower temperatures, where the smallest particles transformed at ~310 °C, only after losing the final (surface) water. Our results highlight the importance of particle size as well as the crystallization conditions on the stability and transformation mechanisms of ACC.
A strain-sensing lyriform organ (HS-10) found on all of the legs of a Central American wandering ... more A strain-sensing lyriform organ (HS-10) found on all of the legs of a Central American wandering spider (Cupiennius salei) detects courtship, prey and predator vibrations transmitted by the plant on which it sits. It has been suggested that the viscoelastic properties of a cuticular pad directly adjacent to the sensory organ contribute to the organ's pronounced high-pass characteristics. Here, we investigate the micromechanical properties of the cuticular pad biomaterial in search of a deeper understanding of its impact on the function of the vibration sensor. These properties are considered to be an effective adaptation for the selective detection of signals for frequencies >40 Hz. Using surface force spectroscopy mapping we determine the elastic modulus of the pad surface over a temperature range of 15-40 °C at various loading frequencies. In the glassy state, the elastic modulus was ~100 MPa, while in the rubbery state the elastic modulus decreased to 20 MPa. These data ar...
Protein-metal interactions--traditionally regarded for roles in metabolic processes--are now know... more Protein-metal interactions--traditionally regarded for roles in metabolic processes--are now known to enhance the performance of certain biogenic materials, influencing properties such as hardness, toughness, adhesion, and self-healing. Design principles elucidated through thorough study of such materials are yielding vital insights for the design of biomimetic metallopolymers with industrial and biomedical applications. Recent advances in the understanding of the biological structure-function relationships are highlighted here with a specific focus on materials such as arthropod biting parts, mussel byssal threads, and sandcastle worm cement.
ABSTRACT Protein-Metall-Wechselwirkungen wurden bisher vor allem hinsichtlich ihrer Bedeutung in ... more ABSTRACT Protein-Metall-Wechselwirkungen wurden bisher vor allem hinsichtlich ihrer Bedeutung in Stoffwechselprozessen betrachtet. Aktuelle Forschungsergebnisse zeigen, dass sie auch die mechanischen Eigenschaften von Biomaterialien verbessern können, wie z. B. Härte, Zähigkeit, Haftung und die Fähigkeit zur Selbstheilung. Die zugrundeliegenden Prinzipien werden hier anhand einiger Beispiele, wie der Beißwerkzeuge von Arthropoden, der Byssusfäden von Miesmuscheln und des Zements von Sandburg-Würmern, besprochen. Diese neuen Erkenntnisse können auch für die Entwicklung von bio-inspirierten Metallopolymeren mit potentiellen Anwendungen in der Industrie und Biomedizin von Bedeutung sein.
ABSTRACT We apply advanced X-ray diffraction techniques at synchrotron microfocus beamlines in or... more ABSTRACT We apply advanced X-ray diffraction techniques at synchrotron microfocus beamlines in order to study the local ultrastructure of biogenic calcite with high spatial and angular resolution. Specifically, we investigate individual calcitic prisms extracted from Pinna nobilis mollusk shells with an aim to shed additional light on the structural aspects of organic/inorganic interfaces. We use annealing at elevated temperatures to destroy intracrystalline organics and measure the same prisms before and after annealing to achieve deeper understanding of the internal organization of these nanobiocomposites. Complementary nanoindentation measurements (also performed before and after annealing) allow us to elucidate the role of intracrystalline organics in increased hardness in pristine prisms and hardness reduction after annealing. We found that removal of intracrystalline organics during annealing facilitates generation of well-oriented lattice defects, which reduce the (006) diffraction intensity and are responsible for the [001]-elongated diffuse streaks nearby diffraction spots. These findings indicate the formation of internal materials discontinuities with smooth and flat interfaces. Such nanodiscontinuities facilitate microcrack propagation under load that explains the reduced hardness of calcitic prisms after annealing.
Journal of the Royal Society, Interface / the Royal Society, Jan 6, 2015
The metatarsal lyriform organ of the Central American wandering spider Cupiennius salei is its mo... more The metatarsal lyriform organ of the Central American wandering spider Cupiennius salei is its most sensitive vibration detector. It is able to sense a wide range of vibration stimuli over four orders of magnitude in frequency between at least as low as 0.1 Hz and several kilohertz. Transmission of the vibrations to the slit organ is controlled by a cuticular pad in front of it. While the mechanism of high-frequency stimulus transfer (above ca 40 Hz) is well understood and related to the viscoelastic properties of the pad's epicuticle, it is not yet clear how low-frequency stimuli (less than 40 Hz) are transmitted. Here, we study how the pad material affects the pad's mechanical properties and thus its role in the transfer of the stimulus, using a variety of experimental techniques, such as X-ray micro-computed tomography for three-dimensional imaging, X-ray scattering for structural analysis, and atomic force microscopy and scanning electron microscopy for surface imaging. ...
X-ray absorption near-edge structure (XANES) spectroscopy and spectromicroscopy have been extensi... more X-ray absorption near-edge structure (XANES) spectroscopy and spectromicroscopy have been extensively used to characterize biominerals. Using either Ca or C spectra, unique information has been obtained regarding amorphous biominerals and nanocrystal orientations. Building on these results, we demonstrate that recording XANES spectra of calcium carbonate at the oxygen K-edge enables polarization-dependent imaging contrast (PIC) mapping with unprecedented contrast, signal-to-noise ratio, and magnification. O and Ca spectra are presented for six calcium carbonate minerals: aragonite, calcite, vaterite, monohydrocalcite, and both hydrated and anhydrous amorphous calcium carbonate. The crystalline minerals reveal excellent agreement of the extent and direction of polarization dependences in simulated and experimental XANES spectra due to X-ray linear dichroism. This effect is particularly strong for aragonite, calcite, and vaterite. In natural biominerals, oxygen PIC-mapping generated high-magnification maps of unprecedented clarity from nacre and prismatic structures and their interface in Mytilus californianus shells. These maps revealed blocky aragonite crystals at the nacre-prismatic boundary and the narrowest calcite needle-prisms. In the tunic spicules of Herdmania momus, O PIC-mapping revealed the size and arrangement of some of the largest vaterite single crystals known. O spectroscopy therefore enables the simultaneous measurement of chemical and orientational information in CaCO3 biominerals and is thus a powerful means for analyzing these and other complex materials. As described here, PIC-mapping and spectroscopy at the O K-edge are methods for gathering valuable data that can be carried out using spectromicroscopy beamlines at most synchrotrons without the expense of additional equipment.
Most biological materials are nanocomposites characterized by a multi-level structural hierarchy.... more Most biological materials are nanocomposites characterized by a multi-level structural hierarchy. Particularly, the arthropod cuticle is a chitin-based composite material where the mechanical properties strongly depend on both molecular chitin/protein properties, and the structural arrangement of chitin-fibrils within the protein matrix. Here materials properties and structural organization of two types of cuticle from distantly related arthropods, the wandering spider Cupiennius salei and American lobster Homarus americanus were studied using nanoindentation and X-ray diffraction. The structural analysis of the two types of cuticle including the packing and alignment of chitin-fibrils is supported by Monte Carlo simulations of the experimental X-ray data, thereby regions of parallel and rotated fibril arrangement can be clearly distinguished. The tip of the spider fang which is used to inject venom into the prey was found to be considerably harder than the lobster carapace, while its stiffness is slightly lower.
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