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Molecular Shape Of Carbonate Ion

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Inorganic materials have essential roles in order, including in building construction, optical devices, mechanical engineering and as biomaterials1,2,three,4. Withal, the industry of inorganic materials is limited by classical crystallization5, which often produces powders rather than monoliths with continuous structures. Several precursors that enable non-classical crystallization—such every bit pre-nucleation clustershalf-dozen,seven,8, dense liquid dropletsix,x, polymer-induced liquid forerunner phases11,12,xiii and nanoparticlesfourteen—have been proposed to better the structure of inorganic materials, but the big-scale awarding of these precursors in monolith preparations is limited by availability and by practical considerations. Inspired by the processability of polymeric materials that can be manufactured by crosslinking monomers or oligomers15, hither we demonstrate the construction of continuously structured inorganic materials past crosslinking ionic oligomers. Using calcium carbonate as a model, we obtain a large quantity of its oligomers (CaCO3) n with controllable molecular weights, in which triethylamine acts as a capping agent to stabilize the oligomers. The removal of triethylamine initiates crosslinking of the (CaCO3) n oligomers, and thus the rapid construction of pure monolithic calcium carbonate and even unmarried crystals with a continuous internal structure. The fluid-like behaviour of the oligomer precursor enables it to be readily candy or moulded into shapes, even for materials with structural complexity and variable morphologies. The material construction strategy that we introduce here arises from a fusion of classic inorganic and polymer chemistry, and uses the same cross-linking procedure for the industry the materials.

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Data availability

The information that support the findings of this report are available from the corresponding author upon reasonable request.

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Acknowledgements

Nosotros thank J. J. De Yoreo, H. Cölfen, P. Fratzl, Due north. A. J. M. Sommerdijk, D. Joester and L. B. Gower for discussions; Y. Li and Y. Qiu for help with SAXS data analysis; C. Yang and B. Wang for assistance with synchrotron SAXS at the Shanghai Synchrotron Radiation Facility; C. Jin, F. Chen, W. Wang and Y. Wang for assistance with electron microscopy; J. Liu for help with XRD; and M. Yu and Y. Liu for assistance with NMR. This work was supported by the National Natural Scientific discipline Foundation of China (21625105 and 21805241) and the China Postdoctoral Science Foundation (2017M621909 and 2018T110585). We thank W. Liu for his assist and inspiration.

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Authors and Affiliations

  1. Department of Chemistry, Zhejiang Academy, Hangzhou, China

    Zhaoming Liu, Changyu Shao, Biao Jin, Yueqi Zhao & Ruikang Tang

  2. Department of Physics, Enquiry Institute for Biomimetics and Soft Affair, Jiujiang Research Establish, Xiamen University, Xiamen, China

    Zhisen Zhang

  3. Qiushi Academy for Advanced Studies, Zhejiang University, Hangzhou, China

    Xurong Xu

  4. State Primal Laboratory of Silicon Materials, Zhejiang University, Hangzhou, Red china

    Ruikang Tang

Contributions

Z.L. and R.T. initiated the project. Z.L. performed the syntheses and the FTIR, MS, NMR and XRD experiments, the calcite repair and conductivity experiments; C.S. carried out the nanoindentation and SEM experiments; B.J. performed the TEM experiments; Z.Z. performed the computer simulations; Y.Z. acquired the synchrotron SAXS and SEM data; R.T. and Z.L. supervised and supported the project; and Z.L. and X.Ten. analysed the data. The manuscript was written past Z.L. and R.T. All authors reviewed and approved the manuscript.

Corresponding writer

Correspondence to Ruikang Tang.

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Competing interests

The authors declare no competing interests.

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Peer review data Nature thanks Kazuo Onuma and the other, anonymous, reviewer(s) for their contribution to the peer review of this piece of work.

Extended information figures and tables

Extended Data Fig. 1 ESI-MS assay of (CaCOthree) n oligomers.

a, Negative-ion mode analysis of CaClii and TEA in ethanol solution. b, Negative-ion fashion assay of (CaCOthree) n oligomers later on v days, indicating that TEA has a long-term stabilization effect. n represents the number of Caii+:COiii ii− units in one (CaCO3) n oligomer. c, d, Positive ion way analysis of CaCltwo and TEA mixed ethanol solution (c) and (CaCOiii) n oligomers (d). east, ESI tandem MS assay of the oligomers with m/z 368, showing only one fragmentation peak at around m/z 260 with negative charges. Because no TEA could be detected in the MS–MS peak (the intensity below m/z 200 is zero), this indicates that no TEA was present in the species with chiliad/z 368.

Extended Information Fig. 2 Synchrotron SAXS, liquid-prison cell TEM, dynamic calorie-free scattering and viscosity analyses of (CaCO3) north oligomers and their aggregates.

a, Handful plots of unlike concentrations of (CaCO3) n measured by synchrotron SAXS. The cherry curve is the plumbing equipment result from DAMMIF. At a concentration of 57.0 mg l−1 an increase in the scattered intensity was detected, and this broad shoulder meridian indicated the aggregation of (CaCO3) n with a big distribution of sizes. A pronounced maxima of the scattered intensity could be observed at a concentration of 285 mg l−ane, demonstrating inter-oligomer correlations induced by the formation of larger (CaCO3) north aggregates. b, Size distribution function of oligomer aggregates at 57.0 mg l−1. The inset shows the simulated shape of aggregates, indicating the beingness of concatenation-like structures, including branches at high concentrations. c, Liquid-cell TEM of the aggregates of the (CaCO3) n oligomers showing a chain-like contrast; the purlieus between the groundwork (blue) and sample (xanthous) is enhanced in the faux color image on the right, and the chain-like aggregates are marked with arrows. d, Viscosity of (CaCOiii) due north oligomers measured at v °C (north ≥ 3). The change in the viscosity with concentration is meliorate fitted with the Huggins equation (R two  = 0.98) than with the Einstein equation (R ii  = 0.94), indicating that the shape of the aggregates in solution was more chain-similar than spherical. east, The hydrodynamic bore of (CaCOthree) n oligomers or their aggregates at different oligomer concentrations measured past dynamic lite handful with a Ca:TEA ratio of ane:xx. The increase (decrease) of the hydrodynamic diameter is reversible by condensing (diluting) the (CaCOthree) north oligomer solution. f, Reversible aggregations and disaggregations of the (CaCO3) northward oligomers revealed past synchrotron SAXS. g, Scheme of the reversible aggregations and disaggregations of the oligomer unit of measurement are controllable past the concentration changes. h, In situ liquid-cell TEM observation of (CaCO3) northward oligomers. The concatenation aggregates remain in dynamical alter (aggregation–disaggregation) states.

Extended Data Fig. 3 FTIR spectra of gel-similar (CaCO3) n oligomers.

a, FTIR spectra showing the tiptop corresponding to the carbonate grouping in (CaCO3) northward . b, The C–Due north bond in TEA. c, The N···H–O bond between TEA and protonated carbonate55. d, The spectra between 400 cm−1 and 4,000 cm−1 are nearly the same for ethanol and gel-like oligomers, which confirms that ethanol is the major component in the gel-like (CaCOiii) n oligomers. e, The peak at 3,340 cm−1 was contributed by the –OH group of ethanol, which obstructed the signal from H in N···H–O. f, The spectrum of ethyl acetate and ethyl acetate-based gel-similar (CaCOiii) due north oligomers. The ethanol had been completely removed from the ethyl acetate-based gel-like (CaCOiii) n oligomers, because the specific peaks of ethanol were non detected; by contrast, the signal at 3,000–4,000 cm−one was detected. g, The peak at three,555 cm−1 was contributed by H in the N···H–O bond.

Extended Data Fig. 4 Molecular dynamics simulation of the TEA-stabilized (CaCO3) due north .

a, Imitation size distribution of (CaCO3) n clusters in the presence and absence of TEA. b, The branch structure in a (CaCO3)five cluster without TEA. The circle shows the branching site. c, The branch structure in the big cluster aggregates without TEA. d, There is no branch structure in a cluster of (CaCOiii)7 with TEA stabilization. e, A branch construction in (CaCO3)15 even with TEA stabilization. These results demonstrate that the stabilization upshot of TEA promotes linear growth of (CaCOthree) n .

Extended Data Fig. 5 (CaCO3) north oligomers in ethanol, DMSO and h2o.

a, d, g, Conductivity of dispersed oligomer solution with ethanol, DMSO or water equally solvent. Later loftier-speed centrifugation and redispersion of (CaCO3) n oligomers in ethanol, DMSO or water, the conductivity of the oligomer solution remained steady at 1.2 μS cm−1 in ethanol (a); the electrical conductivity increased to four.half-dozen μS cm−1 in DMSO and then decreased to 3.8 μS cm−1 within 1 h in DMSO (d); the conductivity increased to 161.2 μS cm−i but rapidly decreased to 72.0 μS cm−1 within 6 min in water (one thousand). b, e, h, oneH NMR measurement of the ethyl grouping of TEA (pure or bound with oligomer) in ethanol (b), DMSO (e) and water (h). The results revealed that the chemical shift of 1H of the ethyl group of pure TEA was 2.56 ppm in ethanol and 2.67 ppm in the oligomer solution (b), and this change in chemical shift can be attributed to the interaction between the TEA and the carbonates in the oligomers. After two days, the unchanged chemic shift of ii.68 ppm corroborated the stable capping effects of the TEA in ethanol. In DMSO (e), ii signals—2.57 and 2.42 ppm—were attributed to bonded and de-bonded TEA, respectively. In water (h), simply the peak for de-bonded TEA in the form of [H-TEA]+ could be detected at 2.83 ppm. c, f, i, Photographs of the (CaCO3) due north materials, which showroom gel-similar features in ethanol and pulverization-similar features in DMSO and water. j–l, 1H NMR measurement of the ethyl group and hydroxyl group of ethanol (pure or bound with oligomer) in ethanol (j), DMSO (g) and water (l). The negligible change in chemic shift proved that no distinct interactions occurred between ethanol and the (CaCO3) northward oligomers.

Extended Data Fig. 6 Cross-linking of (CaCOiii) n oligomers.

a, In situ XRD assay during the drying of (CaCOiii) northward oligomers, showing the evolution from gels to an ACC monolith. b, Evolution of the RDF from gels to an ACC monolith. The acme at around 2.iv Ã… is attributed to Ca–O, and its intensity increased during crosslinking. c, Additional high-resolution TEM images of the crosslinking of (CaCO3) due north upon the removal of TEA, showing the stepwise concatenation growth and branch germination. d, Statistical results of the lengths and fractal dimensions of grown (CaCOthree) northward oligomers. The scheme shows the anisotropic chain growth with branches after TEA removal. east, Cross-linked (CaCOiii) due north with a network structure over an ultra-thin carbon support motion picture. f, EDS analysis of the crosslinked (CaCO3) n in e. g, EDS mapping analysis of the crosslinked CaCO3 oligomers.

Extended Data Fig. 7 Monolithic ACC and other inorganic materials.

a, FTIR assay of the monolithic CaCOiii, showing ACC every bit the only component. b, Thermal gravimetric assay of the monolithic CaCO3, showing a CaCOthree:H2O molar ratio in the ACC of 3:1. c–f, Photographs and XRD patterns of multiple amorphous monoliths, including calcium phosphate (c), calcium sulfate (d), cupric phosphate (e) and manganous phosphate (f) monoliths. The subsequent crystallization manners of these samples are dissimilar. The crystallizations of baggy cupric phosphate and amorphous manganous phosphate cannot be induced by our thermal treatments (700 °C)56. Amorphous calcium phosphate and calcium sulfate tin can transform to hydroxyapatite (c) and gypsum (d), respectively, by using humidity or water treatments. Although large single crystals without cracks have not been obtained, we believe that future improvements in crystallization control may provide a suitable solution. In conclusion, crosslinking oligomers provides a general strategy for the construction of amorphous monoliths with continuous structures, but an appropriate crystallization treatment is as well required to extend the application of this method to the production of crystalline monoliths.

Extended Information Fig. viii Crystallization of ACC under different conditions.

a, FTIR spectra of the monolithic CaCOiii at different time periods under 100% relative humidity at 25 °C. The peaks at 866 cm−one belong to the amorphous phase, and those at 875 cm−i belong to the crystalline phase. The change of the peaks with time indicates a humidity-induced crystallization process. b, Kinetics of phase transformation from ACC to calcite under dissimilar weather condition: <5% relative humidity treatment at 25 °C, 100% relative humidity treatment at 25 °C, 300 °C thermal treatment, and 320 °C thermal treatment. The results show the treatment condition controls for the crystallization. Information technology should exist noted that although single crystals tin exist generated by humidity handling, the size limitation is stricter than that for single crystals generated by thermal treatment. c, Ten-ray diffraction pattern of thermal induced calcite sample measured along <100>, <010>, <001> and <111> zone axes. The indexing rate of our sample was 79%, while that of geological single-crystal calcite was 87%.

Extended Information Fig. 9 Command of thermal-induced crystallization.

a, Scheme of thermal-induced single-crystalline calcite formation. The infrared thermal images show the thermal gradients from the proximal heating site to the distal site during the treatment, which is the cardinal to ensure the oriented crystallization for single-crystal formation. b, POM epitome of a single crystalline calcite. c–i, Thermal treatment at different conditions demonstrating the importance of selecting an appropriate protocol . H, T and C correspond the heating charge per unit, transformation temperature, and cooling rate, respectively. c, d, The continuous motion of the complete amorphous-crystalline crystallization frontier induced by the well-organized thermal gradient with the recommend protocol of H = 1 °C min−1, T = 320 °C and C = v °C min−1. e, XRD pattern of ACC with a protocol of T = 300 °C, showing no crystallization at the depression heating temperature. f, A protocol of H = 1 °C min−one, T = 325 °C and C = 5 °C min−1 results in a interruption of the thermal slope; a spontaneous calcite crystallization is induced at a distal site rather than the amorphous–crystalline crystallization frontier, resulting in polycrystalline formation. one thousand, A protocol of H = 2 °C min−1, T = 320 °C and C = 5 °C min−1 also results in a thermal gradient break so that the random crystallizations occur at the amorphous–crystalline interface. h, A protocol of H = ane °C min−ane, T = 320 °C and C = 10 °C min−1 causes the formation of cracks in the resulting calcite attributable to the fast cooling rate. i, Using the ACC bulk produced by the conventional particle packing, polycrystalline formation is induced after a thermal treatment of H = 1 °C min−1, T = 320 °C and C = 5 °C min−ane, which is attributed to its discontinuous internal structure.

Extended Data Fig. ten Repair of sea-urchin spine and enamel by a combination of the crosslinking oligomers.

a, POM image of natural sea-urchin spine. b, c, SEM images of natural sea-urchin spine, showing the complicated construction with a smooth surface. Inset in c is a cross-sectional view of CaCO3 on the spine. d, ATR-FTIR characterization of the sea-urchin spine, which is inorganic calcite. eastward, POM prototype of the sea-urchin spine grown using the (CaCO3) n oligomers; the crystallization is induced by a simulated sea h2o at 25 °C. f, g, SEM images of the repaired bounding main-urchin spine, which maintains the original complicated construction. A magnified paradigm (k) shows the surface of freshly grown CaCO3. The inset of g is a cross-sectional view of the CaCO3 grown on the spine, demonstrating the continuous interfacial construction between the native sea-urchin spine and the grown calcite. h, ATR-FTIR characterization of the repaired layer on the sea-urchin spine, which is likewise calcite. i, SEM paradigm of the repaired sea-urchin spine using a conventional solution crystallization method. The random precipitation of numerous calcite particles rather than the expected oriented growth is resulted, demonstrating a failure in the biomineral repair. j, Regrowth of enamel construction by using calcium phosphate oligomers and crystallization is induced by simulated oral fluid at 37 °C. Epitaxial growth of the enamel rods is observed, which is due to the continuous construction by the crosslinking oligomers.

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Liu, Z., Shao, C., Jin, B. et al. Crosslinking ionic oligomers equally conformable precursors to calcium carbonate. Nature 574, 394–398 (2019). https://doi.org/x.1038/s41586-019-1645-10

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Source: https://www.nature.com/articles/s41586-019-1645-x

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