Calcite Microneedle Arrays Produced by Inorganic Ion‐Assisted Anisotropic Dissolution of Bulk Calcite Crystal

Long, Xia; Meng, Ruijie; Wu, Weike; Ma, Yurong; Yang, Dong; Qi, Limin

doi:10.1002/chem.201304229

Cited by 9 publications

(13 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is consistent with differences in both dissolution rates, measured from in situ flow-through calcite dissolution experiments using atomic force microscopy (AFM) [22,49,66], and atypical surface morphological features development, as in the presence of NH 4 Cl background ions, which lead to spicule formation on {104} calcite surfaces [67].…”

Section: Influence Of Background Electrolyte Concentrationsupporting

confidence: 81%

Hydration Effects on the Stability of Calcium Carbonate Pre-Nucleation Species

et al. 2017

View full text Add to dashboard Cite

Recent experimental evidence and computer modeling have shown that the crystallization of a range of minerals does not necessarily follow classical models and theories. In several systems, liquid precursors, stable pre-nucleation clusters and amorphous phases precede the nucleation and growth of stable mineral phases. However, little is known on the effect of background ionic species on the formation and stability of pre-nucleation species formed in aqueous solutions. Here, we present a systematic study on the effect of a range of background ions on the crystallization of solid phases in the CaCO 3 -H 2 O system, which has been thoroughly studied due to its technical and mineralogical importance, and is known to undergo non-classical crystallization pathways. The induction time for the onset of calcium carbonate nucleation and effective critical supersaturation are systematically higher in the presence of background ions with decreasing ionic radii. We propose that the stabilization of water molecules in the pre-nucleation clusters by background ions can explain these results. The stabilization of solvation water hinders cluster dehydration, which is an essential step for precipitation. This hypothesis is corroborated by the observed correlation between parameters such as the macroscopic equilibrium constant for the formation of calcium/carbonate ion associates, the induction time, and the ionic radius of the background ions in the solution. Overall, these results provide new evidence supporting the hypothesis that pre-nucleation cluster dehydration is the rate-controlling step for calcium carbonate precipitation.

show abstract

Section: Influence Of Background Electrolyte Concentrationsupporting

confidence: 81%

Hydration Effects on the Stability of Calcium Carbonate Pre-Nucleation Species

et al. 2017

View full text Add to dashboard Cite

show abstract

“…Previous experiments have focused on the use of dissolution strategies to create calcite crystals with surface patterns. Calcite nanoshoot arrays were created via gentle dissolution in undersaturated solutions in the presence of a few selected additives -ammonium iodide and sulfate, 24 ammonium chloride and acetate, 9 and formamide 10 -where this led to nanoshoots with high aspect ratios. Under these conditions dissolution leads to the formation of multiple etch pits over the crystal surface which subsequently increase in size and depth.…”

Section: Additive-directed Changes In Morphology and Surface Patternsmentioning

confidence: 99%

“…7,8 Notably, calcite surfaces patterned with nanoshoots have been generated in the presence of additives using dissolution protocols. 9,10 Again, the surfaces structures formed are expected to reflect the modes of interaction of the additives with the crystal, such that it should be possible to program different surface topographies based on an understanding of the crystal/additive interactions.…”

Section: Introductionmentioning

confidence: 99%

“…While nanostructuring of surfaces is often achieved using top-down lithographic methods, there is enormous potential to use additives, either during crystal growth or dissolution, to create unique surface patterns. Many interesting surface structures have been generated using soluble additives, or by growing crystals in gels. , Notably, calcite surfaces patterned with nanoshoots have been generated in the presence of additives using dissolution protocols. , Again, the surfaces structures formed are expected to reflect the modes of interaction of the additives with the crystal, such that it should be possible to program different surface topographies based on an understanding of the crystal/additive interactions.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Skin-Deep Surface Patterning of Calcite

et al. 2019

View full text Add to dashboard Cite

The influence of soluble additives on the growth of calcite ( CaCO3) is usually rationalized based on changes in crystal morphologies, where preferential association of the additives with either the acute or obtuse steps on the crystal surface gives rise to specific growth forms. In this work we investigate the influence of a highly acidic organic additive with calcite -cp20k from the barnacle Megabalanus rosaand demonstrate that in addition to modifying the crystal morphology, additives can be used to generate calcite crystals with different surface architectures. These can potentially rise to interesting optical effects that may be important in applications such as in coatings and paints. These surface features form during dissolution/reprecipitation at the crystal surface during the incubation of crystals in solution, and confocal fluorescence microscopy confirmed they are limited to the surface of the crystal only. The surface patterning can also be tuned using alternative additives, mixtures of additives and by varying the solution conditions. Notably, we also show that surface structures can be used to determine the mode of interaction of additives with the microscopic surface steps under conditions where only minor changes in morphology have occurred.

show abstract

“…[66] Our previous studies have shown that microneedles along the c-axis may form via oriented dissolution of geological calcite and biogenic calcite minerals in the presence of additive molecules. [67][68][69][70][71][72] Considering the very good biological compatibility, high mechanical properties, ease of synthesis, and high surface area, the calcite microneedle arrays formed on calcite via oriented dissolution are supposed to be good substrates for transdermal delivery. Oriented dissolution is a very convenient and simple method to prepare microneedle arrays, in comparison to the complicated synthetic methods for microneedle-based transdermal delivery such as lithography, electroplating, and wet and dry etching.…”

Section: Introductionmentioning

confidence: 99%

Patterned Calcite Microneedle Arrays formed on Mollusk Shells via Oriented Dissolution and Their Application for Transdermal and Intracellular Delivery

Song

et al. 2022

Adv Materials Inter

Self Cite

View full text Add to dashboard Cite

Transdermal delivery through the skin barriers is an important medical procedure to transfer drugs into the human body. However, there is an urgent requirement to design microneedle‐based transdermal delivery systems with superior delivery efficiency, low toxicity, excellent mechanical property, and simple synthetic process. Herein, perpendicular calcite microneedle arrays with a length of about 8 µm are synthesized on the prism layer of mollusk shells via oriented dissolution while dextran sulfate sodium is applied as an additive. Ordered patterns of long calcite microneedles with a length about 45 µm are synthesized in a large scale for the first time on mollusk prism layers via oriented dissolution while circular masks are covered on the prism layers during the dissolution process. The long calcite microneedle arrays with the ordered pattern are found to be efficient for transdermal delivery of dexamethasone and for therapy of ear psoriasis in mice. The calcite microneedle arrays are also applied to transport Cy3 fluorescent biomolecules through cell membranes in this work. These calcite microneedle arrays can be applied as efficient transportation substrates for both transdermal and intracellular delivery, which exhibit advantages such as high drug loading capacity, superior biocompatibility, nontoxicity, high mechanical properties, and easy synthesis strategy.

show abstract

Calcite Microneedle Arrays Produced by Inorganic Ion‐Assisted Anisotropic Dissolution of Bulk Calcite Crystal

Cited by 9 publications

References 35 publications

Hydration Effects on the Stability of Calcium Carbonate Pre-Nucleation Species

Hydration Effects on the Stability of Calcium Carbonate Pre-Nucleation Species

Skin-Deep Surface Patterning of Calcite

Patterned Calcite Microneedle Arrays formed on Mollusk Shells via Oriented Dissolution and Their Application for Transdermal and Intracellular Delivery

Contact Info

Product

Resources

About