Biomineralization: Principles and Concepts in Bioinorganic Materials Chemistry
Abstract
This book describes the principles and concepts of biomineralization and their application in the new field of biomimetic materials chemistry. The main focus is on the principles and concepts that arise from a chemical perspective of biomineralization. After surveying the major types of biominerals (chapter 2) the general principles of biomineralization are discussed (chapter 3), followed by a detailed description of the chemical aspects of biomineralization (chapter 4). The next four chapters are concerned with the process of biomineralization, including boundary-organized biomineralization (chapter 5), organic matrix-mediated biomineralization (chapter 6), morphogenesis (chapter 7) and biomineral tectonics (chapter 8). The final chapter describes how current knowledge of biomineralization is inspiring new biomimetic strategies in synthetic materials chemistry.
... Metal ion incorporation is a natural phenomenon to develop organic-inorganic hybrid composites with mechanical properties modulation spanning from hard and fracture resistant to soft and tough materials. [1][2][3][4][5][6] Many organisms have mechanisms to produce controlled as well as highly tunable crystalline or amorphous compounds within soft organic matrices by combination with a metal. [7][8][9][10] Cascades of catalytic proteins and ion transport mechanisms actually coordinate by combination of metal and natural scaffolds. ...
... Intriguing the above information, we have shown how calcium-induced gelation of triazole-appended phenylalanine results in stiffness enhancement of the metallogel. The 2,5diphenyl-2H- [1,2,3]triazole-4-carboxylic acid [18] was coupled with L-Phe to develop the gelator 1. This compound typically comprises a hydrophilic carboxylate residue and hydrophobic phenyl rings. ...
... The carboxylic acid functional group will responsive to metal ion. The 2,5diphenyl-2H- [1,2,3]triazole-4-carboxylic acid was synthesized by sequential CÀ N bond formation and electro-oxidative NÀ N coupling under metal-free conditions, starting from readily accessible 2-amino acrylates and aryldiazonium salts (Scheme 1). [18] We coupled L-phenylalanine and triazole derivative to synthesize our target molecule 1 (Scheme 1). ...
Organic‐inorganic hybrid materials are highly important for designing and engineering bioinspired structures and functions. Herein, we have demonstrated the synthesis and metallogelation of triazole‐appended phenylalanine and resulting stiffness enhancement. The 2,5‐diphenyl‐2H‐[1,2,3]triazole‐4‐carboxylic acid was synthesized by sequential C−N bond formation and electro‐oxidative N−N coupling under metal‐free conditions and coupled with L‐Phe to develop the gelator. Starting with basic (pH 11) solutions (5 mg/mL) of gelator, we show that significant stiffness enhancement is achieved upon adding Ca²⁺. From rheology, the storage modulus exhibits 8‐fold increase by the calcium‐induced gelation. The calcium‐induced gels are thixotropic in nature. The calcium ion bivalency leads to “cross‐links” and promote assembly of gelators, which not only influences the gel microstructure but also manipulates subsequent mechanical properties of the metallogels.
... In these cases, the process of mineralization (composition, nucleation, growth, morphology and location) is controlled by cellular activities and is called biologically controlled mineralization. [32,33] In others, mineralization can be induced by secondary reactions leading to favorable conditions to form a mineral such as kidney stones. This type of process, called biologically induced mineralization, [32,33] results in heterogeneity in size, shape and composition of the mineral phase as there is no control from the organism. ...
... [32,33] In others, mineralization can be induced by secondary reactions leading to favorable conditions to form a mineral such as kidney stones. This type of process, called biologically induced mineralization, [32,33] results in heterogeneity in size, shape and composition of the mineral phase as there is no control from the organism. ...
Morphology governs function. Yet, understanding and controlling the emergence of morphology at the molecular level remains challenging. The difficulty in studying the early stage of morphology formation is due to its stochastic nature both spatially and temporally occurring at the nanoscale. This nature has been particularly detrimental for the application of optical spectroscopy. To overcome this problem, we have been developing new in situ/in vivo optical spectroscopy tools, which are label-free and non-invasive. This account highlights several examples of how optical spectroscopy can become an important tool in studying the birth of morphology.
... Mineralized structures are formed by organisms through the process of biomineralization, which dates back about 570 million years ago 48 . Minerals synthesis by microbiota is an environmentally friendly reaction system, without the participation of toxicity chemicals, and can be regarded as green chemistry, showing great potential in biological, biochemical, and biomedical applications as well as industrial benefits. ...
... To explore the generation of Ausome in E. coli, bacterial cells were isolated before and after incubation with HAuCl 4 for 0. 5,4,12,24,48 or 96 h, by centrifuging at 5000× g for 10 min, followed by washing once in PBS and collection via another centrifugation step. Afterwards, the sediment was resuspended to single cells and dropped onto a carbon film-coated copper mesh or a hydrophilization-treated silicon wafer, and naturally dried at room temperature. ...
Manipulating the tumor immune contexture towards a more active state can result in better therapeutic outcomes. Here we describe an easily accessible bacterial biomineralization-generated immunomodulator, which we name Ausome (Au + [exo]some). Ausome comprises a gold nanoparticle core covered by bacterial components; the former affords an inducible hyperthermia effect, while the latter mobilizes diverse immune responses. Multiple pattern recognition receptors actively participate in Ausome-initiated immune responses, which lead to the release of a broad spectrum of pro-inflammatory cytokines and the activation of effector immune cells. Upon laser irradiation, tumor-accumulated Ausome elicits a hyperthermic response, which improves tissue blood perfusion and contributes to enhanced infiltration of immunostimulatory modules, including cytokines and effector lymphocytes. This immune-modulating strategy mediated by Ausome ultimately brings about a comprehensive immune reaction and selectively amplifies the effects of local antitumor immunity, enhancing the efficacy of well-established chemo- or immuno-therapies in preclinical cancer models in female mice.
... 16,18,19,53 Similarly, peptides are known to be active in biomineralization processes and metal nanocrystal synthesis. [54][55][56][57] In both of these examples, peptides are macromolecules that act as surface active agents that control inorganic material growth. Surface-active ligands are necessary components in the synthesis of high-quality nanocrystals. ...
Hybrid organic-inorganic hybrid perovskite (OIP) nanocrystals have gained considerable excitement due to high photoluminescence (PL) quantum yields, bandgap tunability, and narrow band emission, which are essential for photovoltaic devices, light...
... Bivalve shells are among the most highly mineralized materials on earth [1]. These materials achieved extraordinary mechanical and optical properties that are superior to that of artificial materials due to a special hierarchical arrangement of the inorganic components with a low content of organic matrix [2][3][4][5]. The organic matrix within the inorganic component plays an important role in anisotropic distortion mechanisms [6,7]. ...
... As can be seen in Fig. 2, redB shows intermediate characteristics between samples from Type I and III. Moreover, this spectrum shows broader bands than the other five indicating a poor degree of crystallization distinctive of bioapatites (Mann, 2001;Pasteris et al., 2001). Following the study from Wopenka and Pasteris (2005), the broad bands can be attributed to the replacement of phosphate by carbonate which strains the crystal lattice and limits the size of the crystallite growing. ...
... A predominant purpose of carbonate biominerals is protection against predators. In octocorals such as Sarcophyton sp. that lack a skeletal axis, the sclerites allow for the maintenance of a structure and thus form the animal endoskeleton (Mann 2001). ...
In vivo studies of the effects of molecules of interest, such as hormones or xenobiotics on corals, are essential to uncover their effects on coral biological processes. However, exposure to such molecules is very challenging in aquarium systems due to the duration of exposure, the high cost of the compounds, their quantity, and their diffusion in seawater. In this study, we provide a durable alternative method by in vivo injection. The aim of this study was to evaluate slow release and local injection as a novel method of delivering compounds to corals. In this method, coconut oil, which solidifies upon injection and has a melting point of about 24°C, is used as the vehicle for injection. Local diffusion of the injected products in the organism was followed using visual tracers. Specifically, two classes of fluorescent markers were used, one of which examined internalization into cells (rhodamine), while the others were used as an application to monitor the calcification process (alizarin, calcein). In parallel, we developed an analytical method to quantify the calcein and alizarin labeling of sclerites, which allowed us to determine calcification rates in different parts of the coral. Two octocorals were used to optimize these methods, with Sarcophyton sp. being the preferred organism to develop and validate the injection procedures and characterize the diffusion of the markers. Once the method was perfected, injections were performed on the precious coral Corallium rubrum to prove the transferability of the method.
... There are multiple proteinoid-inorganic composites that can be created by taking advantage of various mineral interactions [196]. Silicates facilitate the process of polymerisation and the creation of membranes, whilst clays assist in the organisation of molecules. ...
To understand the origins of life, we must first gain a grasp of the unresolved emergence of the first informational polymers and cell-like assemblies that developed into living systems. Heating amino acid mixtures to their boiling point produces thermal proteins that self-assemble into membrane-bound protocells, offering a compelling abiogenic route for forming polypeptides. Recent research has revealed the presence of electrical excitability and signal processing capacities in proteinoids, indicating the possibility of primitive cognitive functions and problem-solving capabilities. This review examines the characteristics exhibited by proteinoids, including electrical activity and self-assembly properties, exploring the possible roles of such polypeptides under prebiotic conditions in the emergence of early biomolecular complexity. Experiments showcasing the possibility of unconventional computing with proteinoids as well as modelling proteinoid assemblies into synthetic proto-brains are given. Proteinoids’ robust abiogenic production, biomimetic features, and computational capability shed light on potential phases in the evolution of polypeptides and primitive life from the primordial environment.
... These macromolecules provide a template for biofilm organomineralization. Dupraz et al. (2009) later utilized the term "organomineralization sensu lato" for processes not genetically controlled that mediate mineral precipitation on an organic matrix, including in the definition both the active (biologically induced, mediated by living organic substrates) and the passive (biologically influenced, mediated by non-living organic substrates) processes. Summarizing, crystal nucleation in biomineralization processes can be (i) controlled directly by the organisms (Blakemore, 1975;Mann, 1983Mann, , 2001Weiner and Dove, 2003;Bazylinski and Frankel, 2004;Komeili, 2007;Altermann et al., 2009;Riding and Virgone, 2020), (ii) induced by microbial communities (Lowenstam and Weiner, 1989;Perry et al., 2007;Altermann et al., 2009;Dupraz et al., 2009;Borch et al., 2010;Phillips et al., 2013;Anbu et al., 2016;Riding and Virgone, 2020) or (iii) influenced by the presence of cell surface organic matter (Trichet and Défarge, 1995;Perry et al., 2007;Altermann et al., 2009;Dupraz et al., 2009). In all these cases, the formation of biominerals also depends on the chemicalphysical conditions of the environment (Riding and Liang, 2005;Riding, 2011). ...
The coralligenous build-ups located on the Mediterranean shelf in front of Marzamemi (SE Sicily, Italy) represent useful natural examples to use in studying the relationship between skeletal organisms and non-skeletal components in marine bioconstructions. Coralligenous build-ups are formed in open marine systems, and their comparison with coeval bioconstructions (biostalactites) of confined environments, like submarine caves, allows depicting the complex interactions between metazoans and microbial communities in the formations of recent bioconstructions in different Mediterranean settings. In this study, two coralligenous build-ups were characterized in terms of organisms and sediments involved in their formation. The framework mainly consists of coralline algae and subordinate bryozoans and serpulids. Sponges affect the general morphology of the bioconstructions both interacting with skeletonized organisms and through bioerosion activity. The micrite or microcrystalline calcite is present in minor amounts compared to other components that form the build-ups and consists of two types: autochthonous (in situ) and allochthonous (detrital). Fine autochthonous micrite mineralized directly inside the framework cavities and shows aphanitic or peloidal fabric, produced by organomineralization processes of soft sponge tissues and microbial metabolic activity, respectively. The detrital micrite occurring inside cavities derives from external sources or erosion processes of the bioconstructions themselves. This component has been classified as organic or inorganic based on the organic matter contents deduced by UV epifluorescence. A great quantity of sponges live in cavities of the coralligenous build-ups and compete with carbonatogenic bacteria for the same cryptic spaces, limiting the production of microbialites. The sharing of a similar relationship between sponges and microbial communities by coralligenous concretion and biotic crusts of particular submarine caves suggests that this competition is not habitat-specific. On the contrary, it may develop in a range of environmental settings, from open to cryptic systems, and could be used to clarify the role of metazoans vs. microbialites in palaeoecological reconstructions.
... Polymers facilitate kinetic HCO 3 2− entrapment within the dense liquid mineral phase ...
CaCO3 is the most abundant biomineral and a major constituent of incrustations arising from water hardness. Polycarboxylates play key roles in controlling mineralization. Herein, we present an analytical and spectroscopic study of polycarboxylate-stabilized amorphous CaCO3 (ACC) and its formation via a dense liquid precursor phase (DLP). Polycarboxylates facilitate pronounced, kinetic bicarbonate entrapment in the DLP. Since bicarbonate is destabilized in the solid state, DLP dehydration towards solid ACC necessitates the formation of locally calcium deficient sites, thereby inhibiting nucleation. Magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy of poly-aspartate-stabilized ACC reveals the presence of two distinct environments. The first contains immobile calcium and carbonate ions and structural water molecules, undergoing restricted, anisotropic motion. In the second environment, water molecules undergo slow, but isotropic motion. Indeed, conductive atomic force microscopy (C-AFM) reveals that ACC conducts electrical current, strongly suggesting that the mobile environment pervades the bulk of ACC, with dissolved hydroxide ions constituting the charge carriers. We propose that the distinct environments arise from colloidally stabilized interfaces of DLP nanodroplets, consistent with the pre-nucleation cluster (PNC) pathway.
... Но поскольку бактериальная ЩФ была признана индикатором пародонтита, можно предположить сходство механизмов отложения минералов у бактерий и в клетках костной ткани у эукариот (Zorzettoetal., 2023). Однако в костях млекопитающих фосфаты кальция откладываются в виде гидроксиапатита в результате тонко настроенного процесса «биологически контролируемой минерализации», который приводит к образованию функционального материала с высоким уровнем пространственной организации, сложной морфологией и структурой, в отличие от спонтанной «биологически индуцированной минерализации», происходящей у большинства прокариот (Mann, 2001). ЩФ костной ткани катализирует гидролиз полифосфатов и фосфатных эфиров из органических источников (например, алкалоидов и белков) и делает их доступными для взаимодействия с катионами (например, кальцием). ...
... Directing polymorph formation is important for being able to control material properties and is often done through the use of additives. Nature is already an expert in exerting this control, using proteins and organic molecules (acting as additives) to form the different polymorphs of calcium carbonate that make up for example the shells of sea creatures such as mussels and oysters (Lowenstam and Weiner, 1989;Mann, 2001). This so called biomineralized calcium carbonate has many favorable properties such as greater toughness and fracture resistance, created in part by the role of the additives in controlling polymorph and crystal structure. ...
Calcium carbonate is a compound that is well-recognized and very prevalent in daily life e.g., chalk, mussel shells and limescale. However, scientists still have many questions about its formation mechanisms, the different crystal forms it takes, and how we can control and direct this formation to produce this material with different properties. Project M was a chemistry citizen science project for UK secondary schools exploring the synthesis of samples of calcium carbonate under different reaction conditions and analyzing them at Beamline I11, an X-ray diffraction laboratory at the Diamond Light Source synchrotron. Science communication played a crucial role in the success of the project, connecting different communities to the science and creating unique opportunities to center and empower the Project M Scientists.
... Abiotic and biotic components of the Earth are mixed everywhere from the Earth's crust (Bose et al., 2020) to the atmosphere (Delort et al., 2010), and nothing in this envelope can be considered as Unicellular and multicellular organisms take up mineral elements (e.g., Ca, Si and P) in their external environment and typically generate rigid structures constituted mainly of CaPO 4 , CaCO 3 or SiO 2 , most often for the purpose of hardening or stiffening their tissues (Knoll, 2003), for example, bones, osteoderms, teeth, antlers, eggs and shells (Mann, 2001;Murdock & Donoghue, 2011). Intracellular biomineralization widely occurs in cells (Lin et al., 2014), but here for simplicity, we consider only extracellular biomineral structures. ...
We suggest that biogeomorphology should challenge the traditional dichotomy between living and non‐living components of Earth surface systems. To achieve this, biogeomorphologists should gain a better understanding of eco‐evolutionary models and empirical findings developing at the interface between ecology and evolutionary biology. Eco‐evolutionary models explore feedback loops between genes, organisms and the physical or biological components outside the organism's body. This changes our understanding of how organisms interact with their environment and the functional and evolutionary significance of biologically induced landforms. In the niche construction framework, genes can be conceived as the foundational evolutionary units of selection and inheritance, and everything beyond of this unit can be considered as the ‘environment’ for gene expression, either packaged within or unpackaged outside the organism. Both the packaged biological and unpackaged environments can be influenced by genes and manufactured by organisms, respectively, in the form of phenotypes or niche constructions. We propose that biomineralized structures, such as bones, osteoderms, antlers and shells, which can be packaged at varying degrees within an organism, as well as external products of genes such as termite mounds, which are unpackaged at the periphery of the organism, form a gradient of variation in the relative dominance and functional integration of biotic and abiotic components in ecosystems. A more explicit consideration of the functional interrelationships between physical and biological components transcending their traditional boundaries should promote a re‐evaluation of the dichotomy between biological and geomorphological entities.
... Shell organics (raw-OM) consist of inter-and intra-crystalline fractions (inter-and intra-OM). The inter-crystalline phase (i.e., organics located in interstitial spaces between individual biomineral units) forms a framework for the deposition of calcium carbonate, while the intra-crystalline phase becomes entrapped within the individual biomineral units during the shell formation (Mann, 2001;Marin et al., 2007;Meldrum & Cölfen, 2008). Given that inter-and intra-OM differ by formation pathways (Addadi et al., 2006), these two organic pools can vary fundamentally in their macromolecular composition, for example, protein species and hence the relative abundance of AAs (Nudelman et al., 2007). ...
The stable nitrogen isotope composition of bivalve shell organics serves as a proxy for nitrogen fluxes in modern and past ecosystems. An essential prerequisite to reconstruct environmental variables from δ¹⁵N values of bivalve shells is to understand if pristine isotope signals can be retrieved from shell organics after sample pretreatment. δ¹⁵N analyses of fossil shells should be limited to the intra‐crystalline organic matrix (intra‐OM), which is trapped within biomineral units and less likely contaminated or diagenetically overprinted than inter‐crystalline organics (inter‐OM). However, it remains unclear whether the different shell organic phases (insoluble/soluble inter‐OM, intra‐OM) are isotopically distinct and whether δ¹⁵N values of intra‐OM agree with those of bulk organic matter. These questions were tackled by applying different solvents (H2O, HCl, H2O2, NaOCl) to homogenized shell powder of a modern Arctica islandica. Milli‐Q water did not alter bulk δ¹⁵N values indicating the dissolution of the inter‐OM was negligible. Acid‐extracted intra‐OM exhibited a larger isotope variation within replicates and showed a minor but significant fractionation in bulk δ¹⁵N values related to the loss of acid‐soluble components. Compared to H2O2, NaOCl oxidative treatment was more effective in cleaning inter‐OM and produced reliable bulk and amino acid (AA)‐specific δ¹⁵N data of intra‐OM. Furthermore, differences in the relative abundance and δ¹⁵N values of individual AAs suggested that the N isotope composition is not uniform within shells, and the N‐bearing content and AA composition differ between organic phases. Future studies should test the capability of bulk and CSIA‐AA δ¹⁵N proxies in fossil shells as paleoenvironmental archives.
... Moreover, microorganisms can influence and modify the morphology of biominerals, leading to various observed morphologies in microbial mineralization experiments (Fairbairn et al., 2017). In biological processes, organisms exert precise control over mineral formation to produce specific structures, often achieved through the regulation of crystal growth by organic molecules (Addadi & Weiner, 1985;Mann, 2002;Meldrum & Cölfen, 2008). Consequently, significant efforts have been made to identify specific biomolecules associated with particular functions. ...
This study investigates the biomineralization of lead ions by Aspergillus niger from aqueous environments, focusing on the dynamic effects of fungal metabolism and biological components. Three biomolecules (glutamate, methionine, and lysine) were used to induce lead oxalate mineralization under lead stress. Comparative experiments were conducted to analyze the growth characteristics and Pb (II) removal ability of A. niger , as well as the morphological and structural properties of the resulting lead oxalate minerals using inductively coupled plasma atomic emission spectroscopy, X‐ray powder diffraction, and scanning electron microscopy–energy dispersive spectroscopy techniques. The findings reveal that A. niger plays a crucial role in controlling the mineralization process of Pb (II), with biomineralization experiments demonstrating the specific morphogenesis of lead oxalate over time. Additionally, the inclusion of the three biomolecules in the system indirectly influenced the rate of Pb (II) removal and mineral morphology. These results contribute to a better understanding of A. niger ‐mediated biomineralization process of lead oxalate and suggest its potential application in the removal of Pb (II) from aqueous environments, particularly in combination with amino acids for enhanced immobilization and mineral recovery.
Practitioner Points
Fungal activity and amino acids play a crucial role in shaping lead oxalate crystals during water treatment processes.
Specific amino acids can effectively delay lead oxalate recrystallization, enhancing the stability and removal efficiency of the crystals.
Biomineralization mediated by fungi offers a promising and eco‐friendly approach for lead removal and recovery in wastewater treatment.
Exploring the influence of organic additives and fungal metabolism on crystal growth provides valuable insights for developing efficient remediation strategies.
Further research on the utilization of fungi and amino acids can help with innovative and sustainable wastewater treatment technologies.
... 112,113 Interfaces have a critical role in the hierarchical materials, which are usually achieved by joining the elements via gluing or crystal formation as in biomineralization. 114 Materials have been designed to get the desired properties and functionalities via computational modeling based on physi cal and biological understandings of nature, particularly living matter. Metabiomaterials are designer biomaterials with exceptional properties that principally originate from their geometrical designs at different (usu ally smaller) length scales. ...
... Calcium compounds form many polymorphs [3,4,19,22,23], thereby providing an opportunity to use reactants in different structural forms. Tricalcium phosphate exists in four allotropes [23 -26]: the more common forms include amorphous tricalcium phosphate (highest energy), crystalline α-phase (higher energy) and crystalline β-phase (lower energy). ...
Green production of materials is crucial to protect the environment. In this article, a low-temperature steam synthesis strategy for apatite production is shown for limiting chemical pollution and enabling the control of crystallinity. Steam processing produced apatite from calcium carbonate and tricalcium phosphate nanosized powders. Interdiffusion between amorphous precursors gave hydroxyapatite accompanied by calcium-deficient hydroxyapatite. This study unfolds the potential of hydrothermal processing in steam as a synthesis strategy that has been forgotten since the 1950s showing where two solid nanosized powders react to form a new product without creating waste, thereby emulating the clean processing route found in nature. This research reopens the consideration of steam processing for more chemically diverse alternatives and processing of various calcium resources readily available in nature, such as eggshell waste, for greener production. Furthermore, it presents a rarely found combination of apatite forms.
... In addition, they exhibit excellent adsorption capacities for organic molecules (drugs, proteins, or other active species) [47] and various cations (Ca, K, Mg, Zn, etc.) and anion substitutions [48]. These carbonates predominantly found in bone [49]. Calcium phosphate nanoparticles are commonly used for loading and delivery of therapeutic agents at the site of bone injury [50]. ...
Nanotechnology is an interdisciplinary field that includes three highly overlapping areas: nanomaterials, nanoelectronics, and nanobiotechnology. Nanomaterials have revolutionized both therapeutics and diagnostics, as these are emerged as promising candidates which efficiently carry drug molecules. These nanosystems or metallic nanoparticles have increased stability and half-life of drugs, enhanced biodistribution, and carry loaded drug into the required target site. The current review mainly focuses on more environmentally friendly methods to fabricate metal nanocarriers and their surface modifications, such as silver, gold, platinum, ruthenium, palladium, copper, zinc oxide, iron oxide, grapheme oxide. metal sulfides, and nanometal-organic frameworks in drugs. This article signifies role of most efficacious drug delivery systems microemulsions (MEs), cyclodextrin (CD), polymeric nanoparticles (PN), solid lipid nanoparticles (SLNs), nanostructured lipid carriers (NLCs). It focuses on various MNP applications as biological safe drug delivery vehicles. This review describes the applications of various nanocarrier-based delivery systems for more effective treatment of cancer and tumor therapy without side effects.
... These microbial enzymes are synthesize by different microorganism living in variable temperatures, pH, and pressure and support the 'green or biogenic' concept (Bhattacharya and Mukherjee, 2008). These enzymes act intra/extracelluarly (Mann, 2001;Simkiss and Wilbur, 2012). In intracellular mode, they transfer the metal ions inside the cell and reduce them in elemental form. ...
Sustainability and innovation are fundamental to any production system. Providing food to the increasing population
is of paramount importance and is critical to the global stability. However, the issue of food security is facing
stiff challenge from continuously declining soil fertility and scarcity of fertile land. Our reliance on excessive
use of toxic chemical fertilizers for increased yield is major concerns for environment and agriculture's future.
Biofertilizers are gaining traction as a viable alternative to toxic chemical fertilizers, with a market potential of
3.8 billion dollars by 2025. Use of biofertilizer is natural mean to use live microorganisms to improve soil nutritional
status by root surface area expansion, enhanced nutrient availability and acquisition (nitrogen fixation and
phosphate solubilization), production of plant growth promoting substances and inhibition of plant pathogen
growth, and combining all these. Despite being cost-effective and environmentally benign, constraints like inconsistent
supplies and a lack of sufficient quality control is limiting the wide adoption or deployment of biofertilizers.
To make them commercially successful, we need to diversify resource base (i.e., identify and include more viable
strains), create better manufacturing technology, and implement quality control procedures. Use of nanotechnology
in biofertilizer sector via green synthesis or by nanocoating or encapsulation of beneficial microorganism
using nanomaterials is a promising option. Bio-nanofertilizers increase nutrient use efficiency; diminishing
nutrient losses, have multiple crop growth promoting activities and release of nutrients to rate compatible to
plants demand. Adoption and popularization of bio-nanofertilizers require extensive field-testing, public awareness
campaigns, capacity building of resource persons and stakeholders, adaptation of standard production
processes, storage and application, as well as active participation of private organizations and enforcement of
suitable legislation. Here, we discuss before-mentioned issues in light of available evidences and our experience
with India system.
... Calcium carbonate; Synthesis; Albumin; Bio mineralization; Simulation caused by widespread natural processes of calcification and bio mineralization: from bacteria to mammals [4]. Bio composites of various types such as organic/inorganic type of the bio minerals, include a large group of biological o bjects [5]. ...
... Control over biomineralization is one of the most striking features of biological organisms [18]. It is assumed that the presence of organic matter in biominerals can precisely direct the organization of the inorganic crystalline parts during the synthesis of a biomineral composite [19][20][21]. Thus, understanding the molecular organization of a composite structure such as spicules is crucial for understanding their biophysical properties. ...
Caudofoveates are benthic organisms that reside in the deep waters of continental slopes in the world. They are considered to be a group that is of phylogenetic and ecological importance for the phylum Mollusca. However, they remain poorly studied. In this work, we revealed the structure of the spicules of Caudofoveatan mollusks Falcidens sp. The spicules presented a hierarchical organization pattern across different length scales. Various imaging and analytical methods related to light and electron microscopy were employed to characterize the samples. The primary imaging methods utilized included: low voltage field emission scanning electron microscopy (FEG-SEM), focused ion beam-scanning electron microscopy (FIB-SEM), high-resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM), and electron diffraction. In addition, we performed a physicochemical analysis by electron energy loss spectroscopy (EELS) and energy dispersive X-ray spectroscopy (EDS). A crucial factor for successfully obtaining the results was the preparation of lamellae from the spicules without damaging the original structures, achieved using FIB-SEM. This allowed us to obtain diffraction patterns of significant areas of well-preserved sections (lamellae) of the spicules in specific directions and demonstrate for the first time that the bulk of these structures is organized as a single crystal of calcium carbonate aragonite. On the other hand, AFM imaging of the spicules’ dorsal surface revealed a wavy appearance, composed of myriads of small, pointed crystallites oriented along the spicules’ longer axis (i.e., the c-axis of the aragonite). The organization pattern of these small crystallites, the possible presence of twins, the relationship between confinement conditions and accessory ions in the preference for mineral polymorphs, and the single crystalline appearance of the entire spicule, along with the observation of growth lines, provide support for further studies employing Caudofoveata spicules as a model for biomineralization studies.
... Aragonite is one of the most typical phases observed for biomineralized CaCO 3 [1]. After heating, aragonite transforms into calcite prior to the thermal decomposition of CaCO 3 [2][3][4][5][6][7][8]. ...
While heating a seawater spiral shell (Euplica scripta), thermally induced aragonite–calcite (A–C) transformation occurred within the temperature region of multistep thermal dehydration. Here, the kinetic interplay between the A–C transformation and thermal dehydration was studied as a possible cause of the reduction in the A–C transformation temperatures. The kinetics of the A–C transformation was systematically investigated under isothermal conditions by powder X-ray diffractometry and under linear nonisothermal conditions by Fourier transform infrared spectroscopy. The thermal dehydration was characterized as a partially overlapping, three-step process by thermogravimetry–differential thermal analysis coupled with mass spectroscopy for the evolved gases. The A–C transformation occurred in the temperature range of the final part of the second dehydration step and the initial part of the third dehydration step. The kinetics of A–C transformation and thermal dehydration were characterized by contracting geometry-type models, in which the respective transformations were regulated by a constant linear advancement rate and diffusional removal of water vapor, respectively. Based on the kinetic results, the mutual interaction of those thermally induced processes is discussed as a possible cause of the reduction in the A–C transformation temperature.
... In a process referred to as biomineralization, many living organisms orchestrate mineral dissolution, nucleation, crystallization, and phase transformation events to create materials required for their life. 887,889,890,896 Biomineralization occurs in terrestrial and aquatic environments (including physiological fluids) and is a major factor in regulating the biogeochemical character of the planet. Our oxygen-rich atmosphere developed during the Precambrian through interactions of microbial systems with the iron-rich minerals of early Earth. ...
Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by "anomalies" or "non-idealities" such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide- and silicate-water interfaces. This critical review discusses how science progresses from understanding ideal solid-water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. We anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.
Local environments have strict influence over (bio)mineralization in calcifying systems. This snapshot review discusses recent insights into the roles of Ca ²⁺ -macromolecule interactions on the nucleation of calcium carbonate and calcium phosphate minerals. Experimental findings combined with simulations/modeling are providing breakthrough information and raising important questions for future studies. The emerging picture is that both nucleation and growth are driven by local ordering of ions and water about the macromolecule interface, rather than broader properties or molecular class. Tuning macromolecular properties at the atomic scale thus provides opportunities for highly specific controls on mineralization; however, many limitations and challenges remain. We highlight studies employing in-situ atomic force microscopy (AFM) and transmission electron microscopy (TEM) to observe crystallization processes on or near macromolecular substrates. As the distribution and ability of these techniques increases, fundamental studies integrating experimental and computational methods will be crucial to inform a broad range of applications.
Graphical abstract
Plastic pollution in aquatic ecosystems has become a significant problem especially microplastics which can encapsulate into the skeletons of organisms that produce calcium carbonates, such as foraminifera, molluscs and corals....
Calcium oxalate (CaOx) is known to grow on organic matrices and is often associated with the formation of kidney stones. Therefore, it is crucial to understand the nucleation and growth mechanisms. This study investigates the role of electrospun polycaprolactone (PCL)-loaded zarzaparrilla (ZP) (Herreria stellata) in the electrocrystallization (EC) of CaOx. Electrospinning (ES) was used to prepare PCL meshes with random (R) and aligned (A) fiber orientations. CaOx particles were grown directly on conductive tin indium oxide (ITO) glass modified with electrospun ZP-loaded PCL meshes by EC. The CaOx crystals after EC were measured by chronopotentiometry (CP), optical microscopy (OM), scanning electron microscopy (SEM), and X-ray diffraction (XRD), which showed that the ZP additive and PCL fiber orientations are key factors for CaOx nucleation.
The field of nanotechnology has the mysterious capacity to reform every subject it touches. Nanotechnology advancements have already altered a variety of scientific and industrial fields. Nanoparticles (NPs) with sizes ranging from 1 to 100 nm (nm) are of great scientific and commercial interest. Their functions and characteristics differ significantly from those of bulk metal. Commercial quantities of NPs are synthesized using chemical or physical methods. The use of the physical and chemical approaches remained popular for many years; however, the recognition of their hazardous effects on human well-being and conditions influenced serious world perspectives for the researchers. There is a growing need in this field for simple, non-toxic, clean, and environmentally safe nanoparticle production methods to reduce environmental impact and waste and increase energy productivity. Microbial nanotechnology is relatively a new field. Using various microorganisms, a wide range of nanoparticles with well-defined chemical composition, morphology, and size have been synthesized, and their applications in a wide range of cutting-edge technological areas have been investigated. Green synthesis of the nanoparticles is cost-efficient and requires low maintenance. The present review highlights the synthesis of the nanoparticles by different microbes, their characterization, and their biotechnological potential. It further deals with the applications in biomedical, food, and textile industries as well as its role in biosensing, waste recycling, and biofuel production.
Biocompatible magnesium alloys represent revolutionary implantable materials in dentistry and orthopedics but face challenges due to rapid biocorrosion, necessitating protective coatings to mitigate dysfunction. Directly integrating durable protective coatings onto Mg surfaces is challenging because of intrinsic low coating compactness. Herein, inspired by tooth enamel, a novel highly compact dual‐protection inorganic‐protein (inorganicPro) coating is in situ constructed on Mg surfaces through bovine serum albumin (BSA) protein‐boosted reaction between sodium fluoride (NaF) and Mg substrates. The association of Mg ions and BSA establishes a local hydrophobic domain that lowers the formation enthalpy of NaMgF3 nanoparticles. This process generates finer nanoparticles that function as “bricks,” facilitating denser packing, consequently reducing voidage inside coatings by over 50% and reinforcing mechanical durability. Moreover, the incorporation of BSA in and on the coatings plays two synergistic roles: 1) acting as “mortar” to seal residual cracks within coatings, thereby promoting coating compactness and tripling anticorrosion performance, and 2) mitigating fouling‐accelerated biocorrosion in complex biosystems via tenfold resistance against biofoulant attachments, including biofluids, proteins, and metabolites. This innovative strategy, leveraging proteins to alter inorganic reactions, benefits the future coating design for Mg‐based and other metallic materials with tailored anticorrosion and antifouling performances.
Crystallisation pathways of calcium carbonate are strongly influenced by the presence of additives. Through X-ray diffraction, samples made by the Project M Scientists reveal the effect of amino acid and related additives on the crystal structures of calcite and vaterite.
Aim:
This study aimed to understand the morphological effects of (in)organic additives on microbially induced calcium carbonate precipitation (MICP).
Methods and results:
MICP was monitored in real-time in the presence of (in)organic additives: bovine serum albumin (BSA), biofilm surface layer protein A (BslA), magnesium chloride (MgCl2) and poly-L-lysine. This monitoring was carried out using confocal microscopy to observe the formation of CaCO3 from the point of nucleation, in comparison to conditions without additives. Complementary methodologies, namely scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction, were employed to assess the visual morphology, elemental composition, and crystalline structures of CaCO3, respectively, following the crystals' formation. The results demonstrated that in the presence of additives, more CaCO3 crystals were produced at 100 minutes compared to the reaction without additives. The inclusion of BslA resulted in larger crystals than reactions containing other additives, including MgCl2. BSA induced a significant number of crystals from the early stages of the reaction (20 minutes) but did not have a substantial impact on crystal size compared to conditions without additives. All additives led to a higher content of calcite compared to vaterite after a 24-hour reaction, with the exception of MgCl2, which produced a substantial quantity of magnesium calcite.
Conclusions:
The work demonstrates the effect of several (in)organic additives on MICP and sets the stage for further research to understand additive effects on MICP to achieve controlled CaCO3 precipitation.
Biosilica, synthesized annually only by diatoms, is almost 1000 times more abundant than industrial silica. Biosilicification occurs at a high rate, although the concentration of silicic acid in natural waters is ~100 μM. It occurs in neutral aqueous solutions, at ambient temperature, and under the control of proteins that determine the formation of hierarchically organized structures. Using diatoms as an example, the fundamental differences between biosilicification and traditional sol–gel technology, which is performed with the addition of acid/alkali, organic solvents and heating, have been identified. The conditions are harsh for the biomaterial, as they cause protein denaturation and cell death. Numerous attempts are being made to bring sol–gel technology closer to biomineralization processes. Biomimetic synthesis must be conducted at physiological pH, room temperature, and without the addition of organic solvents. To date, significant progress has been made in approaching these requirements. The review presents a critical analysis of the approaches proposed to date for the silicification of biomacromolecules and cells, the formation of bionanocomposites with controlled structure, porosity, and functionality determined by the biomaterial. They demonstrated the broad capabilities and prospects of biomimetic methods for creating optical and photonic materials, adsorbents, catalysts and biocatalysts, sensors and biosensors, and biomaterials for biomedicine.
Separation technology of organic compounds using mesoporous materials has been widely used in the fields of analytical chemistry, pharmacy, and engineering. Characterizing of the hydration state of solute in a confined solution is necessary to improve the separation and purification technology using pores. In the present study, differential scanning calorimetry, X-ray diffraction, and quasi-elastic neutron scattering（QENS）measurements of aqueous glycine solutions confined in mesoporous silica（MCM-41）showed that glycine molecules locate near the pore surface of MCM-41 due to the formation of hydrogen bonding between glycine molecules and the silanol group of the MCM-41 wall at pH＝5. It is in contrast to the case at pH＝2.
Understanding biomineralization relies on imaging chemically heterogeneous organic–inorganic interfaces across a hierarchy of spatial scales. Further, organic minority phases are often responsible for emergent inorganic structures from the atomic arrangement of different polymorphs, to nano- and micrometer crystal dimensions, up to meter size mollusk shells. The desired simultaneous chemical and elemental imaging to identify sparse organic moieties across a large field-of-view with nanometer spatial resolution has not yet been achieved. Here, we combine nanoscale secondary ion mass spectroscopy (NanoSIMS) with spectroscopic IR s -SNOM imaging for simultaneous chemical, molecular, and elemental nanoimaging. At the example of Pinctada margaritifera mollusk shells we identify and resolve ~ 50 nm interlamellar protein sheets periodically arranged in regular ~ 600 nm intervals. The striations typically appear ~ 15 µm from the nacre-prism boundary at the interface between disordered neonacre to mature nacre. Using the polymorph distinctive IR-vibrational carbonate resonance, the nacre and prismatic regions are consistently identified as aragonite ( $${\overline{\nu }}_{a}=860$$ ν ¯ a = 860 cm ⁻¹ ) and calcite ( $${\overline{\nu }}_{c}=880$$ ν ¯ c = 880 cm ⁻¹ ), respectively. We observe previously unreported morphological features including aragonite subdomains encapsulated in extensions of the prism-covering organic membrane and regions of irregular nacre tablet formation coincident with dispersed organics. We also identify a ~ 200 nm region in the incipient nacre region with less well-defined crystal structure and integrated organics. These results show with the identification of the interlamellar protein layer how correlative nano-IR chemical and NanoSIMS elemental imaging can help distinguish different models proposed for shell growth in particular, and how organic function may relate to inorganic structure in other biomineralized systems in general.
Human beings have always used natural forms as inspiration for the design of their space. Today, technology has improved the integration of natural forms in architecture and has allowed designers to achieve more complex forms found in nature. The present study focuses on one of the most important sources of inspiration from nature, i.e. synclastic surfaces and explicates how the formal and structural concepts of these surfaces are used in architecture compared to other surfaces. The research method of this paper is comparative and descriptive-analytical, and it uses primary resources and examples to show how the form and structure of natural synclastic surfaces can influence contemporary architecture.
Mollusks, as well as many other living organisms, have the ability to shape mineral crystals into unconventional morphologies and to assemble them into complex functional mineral–organic structures, an observation that inspired tremendous research efforts in scientific and technological domains. Despite these, a biochemical toolkit that accounts for the formation of the vast variety of the observed mineral morphologies cannot be identified yet. Herein, phase‐field modeling of molluscan nacre formation, an intensively studied biomineralization process, is used to identify key physical parameters that govern mineral morphogenesis. Manipulating such parameters, various nacre properties ranging from the morphology of a single mineral building block to that of the entire nacreous assembly are reproduced. The results support the hypothesis that the control over mineral morphogenesis in mineralized tissues happens via regulating the physico‐chemical environment, in which biomineralization occurs: the organic content manipulates the geometric and thermodynamic boundary conditions, which in turn, determine the process of growth and the form of the biomineral phase. The approach developed here has the potential of providing explicit guidelines for the morphogenetic control of synthetically formed composite materials.
Nanotechnology is concerned with the creation and stabilisation of nanoparticles. The biological method necessitates the creation of nanoparticles that are eaten by microorganisms capable of digesting nanoparticles in various forms. The fungus Pestaloptiopsis breviseta is used in this study to demonstrate the extracellular production of stable silver nanoparticles. The fungal culture was isolated from a stable Catharanthus roseus (L) G.don leaf sample, a common therapeutic plant. They were produced after the AgNO3 solution was employed to treat the cell filtrate and the fungal mat at room temperature and in the dark. (1 mM). The cell filtrate made silver nanoparticles that were between 171-378 nm in size, whereas the fungal biomass was between 140-280 nm in size. The cell lines MCF-7 and A549 were likewise treated with the silver nanoparticles made by the fungi. GraphPad Prism 5 software was used to track the percentage of living cells for 24 and 48 hours at different concentrations of the MCF-7 and A549 cell lines based on the IC50 value.
Bone has a complex hierarchical structure with structural integration from nm to cm. The understanding of bone structure is developing rapidly due to improvements in available methodologies that allow unravelling structures across several length scales. These methods include advances in electron microscopy, in particular, focused ion beam scanning electron microscopy (FIB‐SEM), confocal laser scanning microscopy techniques, X‐ray imaging, X‐ray diffraction tomography (XRD‐CT), and tensor tomography (small angle X‐ray scattering tensor tomgraphy, SAXS‐TT and wide angle X‐ray scattering tensor tomgraphy, WAXS‐TT). Special emphasis is placed on the latter X‐ray techniques that are emerging into powerful tools. Through a review of selected recent results on the structure of the bone matrix as well as the lacuno‐canalicular network housing the osteocyte cells of bone, it is proposed that bone is more heterogeneous than typically described and that local variation in composition and crystallography may play a significant role in bone biology in health and disease.
The subject of biomineralogy is the in vivo formation of minerals by living organisms. Biominerals are thus all mineral components that are formed by the activity of various life forms. Biomineralization has been known for about 2 billion years. Early witnesses of biomineralization are considered to be terrestrial magnetofossils, which dominated these mineralization processes mainly through the crystallization of magnetite (Fe3O4). The explosive proliferation of a wide variety of life forms from the Cambrian onwards subsequently resulted in the formation of Ca-bearing biominerals such as carbonates and phosphates, as well as SiO2 mineralizations. Biominerals serve as mechanical strength and stabilization of organic structures (e.g., skeleton), protective function, comminution tool, magnetic, optical and gravity sensors, and storage medium. Following natural biominerals, biomaterials are now used in many areas of medicine and medical technology. The chapter provides an overview of principles of biomineralization, natural biomineral systems and engineered biomaterials and their production.
Nanotechnology, the new era in the field of science and technology, has revolutionized a wide range of research ideas and is still evolving at an extraordinary rate. Moreover, the field of microbiology has also contributed lots of novel solutions for human welfare while keeping the ecological and environmental balance in a correct way. On the contrary, multiple drug resistance (MDR) in microorganisms is a serious threat to all the living organisms at the present time due to inappropriate or frequent use of drugs and it has emerged as one of the preeminent public health concerns of the twenty-first century. Therefore, it is an urgent need to widen the interdisciplinary research practices so that researchers can provide some innovative ideas for well-being of human as well as environment. Nanotechnology provides development and application of materials at a nanoscale (10−9 m) in the form of nanoparticles and offers marked use in antimicrobial agents, nano-drugs, diagnostics, etc., for better treatment of diseases. Thus, combining these two disciplines, i.e., nanotechnology and microbiology, will definitely pave a way of promising result. This chapter discusses the boom of nanotechnology and relates with the field of microbiology to assist mankind through an array of applications in different fields, namely, water, soil, and medical microbiology.KeywordsNanotechnologyMicrobiologyNanoparticlesBionanomaterialsNanobioremediation
Precipitation of calcium carbonate in bulk solutions is well known to result in a bell-shaped or bimodal particle size distribution. However, it is unclear how the distribution behaves if precipitation occurs in a small, confined volume. In this Letter, we conduct microfluidic experiments where sodium carbonate and calcium chloride solutions are continuously injected into a microchannel to precipitate calcium carbonate particles. Results show that, regardless of the variations in reagent concentrations, mixing schemes, flow rates, and precipitation time, sizes of precipitated particles in the channel are power law distributed, with an exponent of 1.4. The data are described by an extended Yule process with the introduction of a ripening term. Since the Yule process is a general mechanism for power law generation, the extended Yule process proposed here provides a general model for systems where growth and ripening simultaneously present.
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