A Descriptive Review on the Potential Use of Diatom Biosilica as a Powerful Functional Biomaterial: A Natural Drug Delivery System.

Although various chemically synthesized materials are essential in medicine, food, and agriculture, they can exert unexpected side effects on the environment and human health by releasing certain toxic chemicals. Therefore, eco-friendly and biocompatible biomaterials based on natural resources are being actively explored. Recently, biosilica derived from diatoms has attracted attention in various biomedical fields, including drug delivery systems (DDS), due to its uniform porous nano-pattern, hierarchical structure, and abundant silanol functional groups. Importantly, the structural characteristics of diatom biosilica improve the solubility of poorly soluble substances and enable sustained release of loaded drugs. Additionally, diatom biosilica predominantly comprises SiO2, has high biocompatibility, and can easily hybridize with other DDS platforms, including hydrogels and cationic DDS, owing to its strong negative charge and abundant silanol groups. This review explores the potential applications of various diatom biosilica-based DDS in various biomedical fields, with a particular focus on hybrid DDS utilizing them.

Nanopatterns on silica scales of Mallomonas (Chrysophyceae, Stramenopiles): Unraveling UV resistance potential and diverse response to UVA and UVB radiation.

Mallomonas thrive primarily in freshwaters and dominate plankton communities, especially in oligotrophic waters. The cells have a siliceous cell covering of regularly arranged scales. Despite their ecological importance, the intricate structure and evolutionary significance of their silica scales are still unexplored. We investigated the nanopatterns on the scales and hypothesized that they may play a role in UV shielding. UVA and UVB exposure experiments were performed with 20 Mallomonas species, categorized into four groups based on the nanopattern of the scales (plain-scaled, meshed, striated, and papilliferous group); a fifth group consisted of the species that have extremely thick, robust scales regardless of the nanopattern. We revealed that thick scales were associated with enhanced UVB resistance, suggesting a protective role. No significant differences in UVA response were observed among the groups, except for the meshed group, which showed lower resistance, likely due to the less regular pattern on the shield. In conclusion, the scale case, composed of sufficiently silicified scales, provides effective UV protection in freshwater environments, regardless of the particular nanopattern. In increased UVB radiation, the thickness of the scales plays role. Contrary to expectations, cell size and phylogeny do not strongly predict UV resistance. The study highlights the diverse UV responses of Mallomonas, but further studies are needed to understand the role of scales/nanopatterns in the ecological adaptations of the species.

Improving Recovery of Diatoms Bio-Silica Using Chemical Treatment with VAUS TM.

High-temperature baking is a typical method to remove organic matter from diatoms, but it's not suitable for bio-silica because of the high crystallinity. This study provides a method using the VAUS™ to remove organic matter from diatoms more quickly and biocompatibly. Organic matter was removed by using VAUS™, while NaOCl was utilized to remove the organic matter from the silicate frustule. The optimal frequency for organic matter removal was investigated to domestically produced M. nummuloides. The removal efficiency of TOC/TN was calculated and analyzed. The C and Si elements were analyzed in EDS, while visual confirmation of organic matter removal was analyzed by using XRD. TOC RE% at a frequency of 35kHz exhibited the highest value, indicating a statistically significant difference. XRD analysis demonstrated that the organic matter was almost removed using NaOCl compared to the high-temperature baked M. nummuloides. In the EDS analysis, there were significant differences in the C and Si elements with respect to frequency. This is very similar to the values from the positive control group, high-temperature baked M. nummuloides. This new procedure of applying periodic negative pressure to NaOCl pre-treatment is considered to be an effective method of chemically removing organic matter from diatoms.

Simultaneous Effect of Diameter and Concentration of Multi-Walled Carbon Nanotubes on Mechanical and Electrical Properties of Cement Mortars: With and without Biosilica.

In this work, the effect of multi-walled carbon nanotubes (MWCNT1, MWCNT2, and MWCNT3) with different outer diameters and specific surface areas on the mechanical and electrical properties of cement mortar have been investigated. Various concentrations of MWCNTs were used (0.05, 0.10, and 0.15%), the effective dispersion of which was carried out by an Ultrasonic machine (for 40 min with 160 W power and a 24 kHz frequency) using a surfactant. Composites have been processed with a biosilica content of 10% by weight of cement and without it. Compressive strength tests were carried out on days 7 and 28 of curing. The 7-day compressive strength of samples prepared without biosilica increased compared to the result of the control sample (6.4% for MWCNT1, 7.4% for MWCNT2, and 10.8% for MWCNT3), as did those using biosilica (6.7% in the case of MWCNT1, 29.2% for MWCNT2, and 2.1% for MWCNT3). Compressive strength tests of 28-day specimens yielded the following results: 21.7% for MWCNT1, 3.8% for MWCNT2, and 4.2% for MWCNT3 in the absence of biosilica and 8.5%, 12.6%, and 6.3% with biosilica, respectively. The maximum increase in compressive strength was observed in the composites treated with a 0.1% MWCNT concentration, while in the case of 0.05 and 0.15% concentrations, the compressive strengths were relatively low. The MWCNT-reinforced cement matrix obtained electrical properties due to the high electrical conductivity of these particles. The effect of MWCNT concentrations of 0.05, 0.10, and 0.15 wt% on the electrical properties of cement mortar, especially the bulk electrical resistivity and piezoresistive characteristics of cement mortar, was studied in this work. At a concentration of 0.05%, the lowest value of resistivity was obtained, and then it started to increase. The obtained results show that all investigated specimens have piezoresistive properties and that the measurements led to a deviation in fractional change in resistivity.

In Vivo Effects of Biosilica and Spongin-Like Collagen Scaffolds on the Healing Process in Osteoporotic Rats.

Due to bioactive properties, introducing spongin-like collagen (SPG) into the biosilica (BS) extracted from marine sponges would present an enhanced biological material for improving osteoporotic fracture healing by increasing bone formation rate. Our aim was to characterize the morphology of the BS/SPG scaffolds by scanning electron microscopy (SEM), the chemical bonds of the material by Fourier transform infrared spectroscopy (FTIR), and evaluating the orthotopic in vivo response of BS/SPG scaffolds in tibial defects of osteoporotic fractures in rats (histology, histomorphometry, and immunohistochemistry) in two experimental periods (15 and 30 days). SEM showed that scaffolds were porous, showing the spicules of BS and fibrous aspect of SPG. FTIR showed characteristic peaks of BS and SPG. For the in vivo studies, after 30 days, BS and BS/SPG showed a higher amount of newly formed bone compared to the first experimental period, observed both in the periphery and in the central region of the bone defect. For histomorphometry, BS/SPG presented higher %BV/TV compared to the other experimental groups. After 15 days, BS presented higher volumes of collagen type I. After 30 days, all groups demonstrated higher volumes of collagen type III compared to volumes at 15 days. After 30 days, BS/SPG presented higher immunostaining of osteoprotegerin compared to the other experimental groups at the same experimental period. The results showed that BS and BS/SPG scaffolds were able to improve bone healing. Future research should focus on the effects of BS/SPG on longer periods in vivo studies.

Antimicrobial and Hemostatic Diatom Biosilica Composite Sponge.

The 3D nanopatterned silica shells of diatoms have gained attention as drug delivery vehicles because of their high porosity, extensive surface area, and compatibility with living organisms. Tooth extraction may result in various complications, including impaired blood clotting, desiccation of the root canal, and infection. Therapeutic sponges that possess multiple properties, such as the ability to stop bleeding and kill bacteria, provide numerous advantages for the healing of the area where a tooth has been removed. This study involved the fabrication of a composite material with antibacterial and hemostatic properties for dental extraction sponges. We achieved this by utilizing the porous nature and hemostatic capabilities of diatom biosilica. The antibiotic used was doxycycline. The gelatin-based diatom biosilica composite with antibiotics had the ability to prevent bleeding and release the antibiotic over a longer time compared to gelatin sponge. These properties indicate its potential as a highly promising medical device for facilitating rapid healing following tooth extraction.

Soil remediation and nano-biosilica: a potential combination to improve the environmental quality of brackishwater aquaculture ponds affected by acid sulfate soils.

The successful management of ASS-affected brackishwater aquaculture ponds necessitates overcoming associated environmental limitations. This study investigated the potential application of nano-biosilica from rice husk ash (RHA) and soil remediation techniques to improve the environmental quality of ASS-affected brackishwater ponds. The study followed a completely randomized design (CRD) with four treatments and three replicates. The treatments comprised applying soil remediation, nano-biosilica fertilizer, and their combination. The study generally revealed that the combination of soil remediation technique and RHA-driven nano-biosilica improved the water quality of ASS-affected brackishwater ponds. Soil remediation improved water quality by reducing acidity levels. However, excessive lime application as an integral part of the remediation might release acidity and toxic metals into water, potentially increasing calcium-phosphorus fixation. Despite liming potential negative consequences, if mixed with nano-biosilica could increase diatom-phytoplankton growth by reducing dissolved Al and Fe levels while boosting P and Si availability. Liming could also help boost diatom photosynthesis and inhibit unwanted algae blooms by decreasing water turbidity and increasing sunlight penetration. This study emphasized that the effectiveness of nano-biosilica in promoting diatom growth depends on appropriate nitrogen (N) and phosphorus (P) concentrations and ratios, which should not be a limiting factor. However, the required N/P concentration and ratio are only met if the remediation method is effectively implemented. The combination of nano-biosilica and soil remediation treatment maintained SiO2 concentrations above the average natural seawater concentration; however, availability may be limited due to complexes containing Ca, Al, Mg, and Fe. Regularly applying cost-effective nano-biosilica fertilizer in combination with N and P fertilizers is recommended to enhance water remediation efficiency by boosting Si availability and decreasing the toxicity of dissolved toxic metal ions.

Enhancing Maize Yield and Quality with Metal-Based Nanoparticles without Translocation Risks: A Brief Field Study.

Our previous studies have shown physiological and yield intensification of selected crops with the application of nanoparticles (NPs). However, the impact on the quantitative, qualitative, and yield parameters of maize (Zea mays L.) in field conditions remains highly debated. This study aimed to evaluate the effects of zinc oxide (ZnO-NPs), gold NPs anchored to meso-biosilica (Au-NP-bioSi), and titanium dioxide (TiO2-NPs) as biological stimulants under field conditions during the vegetation season of 2021 in the Central European region. The study assessed the effects on the number of plants, yield, yield components, and nutritional quality, including mineral nutrients, starch, and crude protein levels. The potential translocation of these chemically-physically stable NPs, which could pose a hazard, was also investigated. The results indicate that Au-NP-bioSi and ZnO-NPs-treatments were the most beneficial for yield and yield components at a statistically significant level. Mineral nutrient outcomes were varied, with the NP-free variant performing the best for phosphorus-levels, while Au-NP-bioSi and ZnO-NPs were optimal for crude protein. Starch content was comparable across the TiO2-NPs, Au-NP-bioSi, and control variants. Importantly, we observed no hazardous translocation of NPs or negative impacts on maize grain quality. This supports the hypothesis that NPs can serve as an effective tool for precise and sustainable agriculture.

Silactins and Structural Diversity of Biosilica in Sponges.

Sponges (phylum Porifera) were among the first metazoans on Earth, and represent a unique global source of highly structured and diverse biosilica that has been formed and tested over more than 800 million years of evolution. Poriferans are recognized as a unique archive of siliceous multiscaled skeletal constructs with superficial micro-ornamentation patterned by biopolymers. In the present study, spicules and skeletal frameworks of selected representatives of sponges in such classes as Demospongiae, Homoscleromorpha, and Hexactinellida were desilicified using 10% HF with the aim of isolating axial filaments, which resemble the shape and size of the original structures. These filaments were unambiguously identified in all specimens under study as F-actin, using the highly specific indicators iFluor™ 594-Phalloidin, iFluor™ 488-Phalloidin, and iFluor™ 350-Phalloidin. The identification of this kind of F-actins, termed for the first time as silactins, as specific pattern drivers in skeletal constructs of sponges opens the way to the fundamental understanding of their skeletogenesis. Examples illustrating the biomimetic potential of sophisticated poriferan biosilica patterned by silactins are presented and discussed.

3D printed scaffolds of biosilica and spongin from marine sponges: analysis of genotoxicity and cytotoxicity for bone tissue repair.

Biosilica (BS) and spongin (SPG) from marine sponges are highlighted for their potential to promote bone regeneration. Moreover, 3D printing is introduced as a technology for producing bone grafts with optimized porous structures, allowing for better cell attachment, proliferation, and differentiation. Thus, this study aimed to characterize the BS and BS/SPG 3D printed scaffolds and to evaluate the biological effects in vitro. The scaffolds were printed using an ink containing 4 wt.% of sodium alginate. The physicochemical characteristics of BS and BS/SPG 3D printed scaffolds were analyzed by SEM, EDS, FTIR, porosity, evaluation of mass loss, and pH measurement. For in vitro analysis, the cellular viability of the MC3T3-E1 cell lineage was assessed using the AlamarBlue® assay and confocal microscopy, while genotoxicity and mineralization potential were evaluated through the micronucleus assay and Alizarin Red S, respectively. SEM analysis revealed spicules in BS, the fibrillar structure of SPG, and material degradation over the immersion period. FTIR indicated peaks corresponding to silicon oxide in BS samples and carbon oxide and amine in SPG samples. BS-SPG scaffolds exhibited higher porosity, while BS scaffolds displayed greater mass loss. pH measurements indicated a significant decrease induced by BS, which was mitigated by SPG over the experimental periods. In vitro studies demonstrated the biocompatibility and non-cytotoxicity of scaffold extracts. .Also, the scaffolds promoted cellular differentiation. The micronucleus test further confirmed the absence of genotoxicity. These findings suggest that 3D printed BS and BS/SPG scaffolds may possess desirable morphological and physicochemical properties, indicating in vitro biocompatibility.

Diatom Biosilica Functionalised with Metabolically Deposited Cerium Oxide Nanoparticles.

This study introduces a novel approach to synthesising a three-dimensional (3D) micro-nanostructured amorphous biosilica. The biosilica is coated with cerium oxide nanoparticles obtained from laboratory-grown unicellular photosynthetic algae (diatoms) doped metabolically with cerium. This unique method utilises the ability of diatom cells to absorb cerium metabolically and deposit it on their silica exoskeleton as cerium oxide nanoparticles. The resulting composite (Ce-DBioSiO2) combines the unique structural and photonic properties of diatom biosilica (DBioSiO2) with the functionality of immobilised CeO2 nanoparticles. The kinetics of the cerium metabolic insertion by diatom cells and the physicochemical properties of the obtained composites were thoroughly investigated. The resulting Ce-DBioSiO2 composite exhibits intense Stokes fluorescence in the violet-blue region under ultraviolet (UV) irradiation and anti-Stokes intense violet and faint green emissions under the 800 nm near-infrared excitation with a xenon lamp at room temperature in an ambient atmosphere.

Osteoblast responsive biosilica-enriched gelatin microfibrillar microenvironments.

Engineering of scaffolds for bone regeneration is often inspired by the native extracellular matrix mimicking its composite fibrous structure. In the present study, we used low loadings of diatomite earth (DE) biosilica to improve the bone regeneration potential of gelatin electrospun fibrillar microenvironments. We explored the effect of increasing the DE content from 1 % to 3 % and 5 %, respectively, on the physico-chemical properties of the fibrous scaffolds denoted FG_DE1, FG_DE3, FG_DE5, regarding the aqueous media affinity, stability under simulated physiological conditions, morphology characteristics, and local mechanical properties at the surface. The presence of biosilica generated composite structures with lower swelling degrees and higher stiffness when compared to gelatin fibers. Increasing DE content led to higher Young modulus, while the stability of the protein matrix in PBS, at 37 °C, over 21 was significantly decreased by the presence of diatomite loadings. The best preosteoblast response was obtained for FG_DE3, with enhanced mineralization during the osteogenic differentiation when compared to the control sample without diatomite. 5 % DE in FG_DE5 proved to negatively influence cells' metabolic activity and morphology. Hence, the obtained composite microfibrillar scaffolds might find application as osteoblast-responsive materials for bone tissue engineering.

The Role of Lysozyme in the Formation of Bioinspired Silicon Dioxide.

Several organisms are able to polycondensate tetraoxosilicic(IV) acid to form silicon(IV) dioxide using polycationic molecules. According to an earlier mechanistic proposal, these molecules undergo a phase separation and recent experimental evidence appears to confirm this model. At the same time, polycationic proteins like lysozyme can also promote polycondensation of silicon(IV) dioxide, and they do so under conditions that are not compatible with liquid-liquid phase separation. In this manuscript we investigate this conundrum by molecular simulations.

Microalgae derived honeycomb structured mesoporous diatom biosilica for adsorption of malachite green: Process optimization and modeling.

The present study investigated the removal of malachite green dye from aquifers by means of microalgae-derived mesoporous diatom biosilica. The various process variables (dye concentration, pH, and adsorbent dose) influencing the removal of the dye were optimized and their interactive effects on the removal efficiency were explored by response surface methodology. The pH of the solution (pH = 5.26) was found to be the most dominating among other tested variables. The Langmuir isotherm (R2 = 0.995) best fitted the equilibrium adsorption data with an adsorption capacity of 40.7 mg/g at 323 K and pseudo-second-order model (R2 = 0.983) best elucidated the rate of dye removal (10.6 mg/g). The underlying mechanism of adsorption was investigated by Weber-Morris and Boyd models and results revealed that the film diffusion governed the overall adsorption process. The theoretical investigations on the dye structure using DFT-based chemical reactivity descriptors indicated that malachite green cations are electrophilic, reactive and possess the ability to accept electrons, and are strongly adsorbed on the surface of diatom biosilica. Also, the Fukui function analysis proposed the favorable adsorption sites available on the adsorbent surface.

Thermo-sensitive hydroxybutyl chitosan/diatom biosilica hydrogel with immune microenvironment regulatory for chronic wound healing.

This study proposes a chronic wound therapeutic strategy based on extracellular matrix (ECM) biomimetics and immune regulation. The hydroxybutyl chitosan/diatom biosilica hydrogel (H/D) which can regulate the immune microenvironment, is prepared from hydroxybutyl chitosan (HBC) as matrix to construct the bionic ECM and diatom biosilica (DB) as structural active unit. The hierarchical porous structure of DB provides strong anchoring interface effect to enhance the mechanical strength of hydrogel, while maintaining its favorable temperature phase transition behavior, improving the material's fit to the wound and convenience of clinical use. Silicates released from DB in H/D accelerate the transition of wounds from inflammation to proliferation and remodeling. In cellular and diabetic rat models, H/D reduces inflammation (induces conversion of M1-type macrophages to M2-type), induces angiogenesis (1.96-fold of control), promotes fibroblast proliferation (180.36 % of control), collagen deposition, keratinocyte migration (47.34 % more than control), and re-epithelialization. This study validates a possible biological mechanism for H/D bioactive hydrogel-mediated regulation of the immune microenvironment and provides a simple synergistic dressing strategy.

Biomimetic Diatom Biosilica and Its Potential for Biomedical Applications and Prospects: A Review.

Diatom biosilica is an important natural source of porous silica, with three-dimensional ordered and nanopatterned structures referred to as frustules. The unique features of diatom frustules, such as their high specific surface area, thermal stability, biocompatibility, and adaptable surface chemistry, render diatoms valuable materials for high value-added applications. These attributes make diatoms an exceptional cost-effective raw material for industrial use. The functionalization of diatom biosilica surface improves its biophysical properties and increases the potential applications. This review focuses on the potential uses of diatom biosilica including traditional approaches and recent progress in biomedical applications. Not only well-studied drug delivery systems but also promising uses on bone regeneration and wound healing are covered. Furthermore, considerable aspects and possible future directions for the use of diatom biosilica materials are proposed to develop biomedical applications and merit further exploration.

The Physiological Inorganic Polymers Biosilica and Polyphosphate as Key Drivers for Biomedical Materials in Regenerative Nanomedicine.

There is a need for novel nanomaterials with properties not yet exploited in regenerative nanomedicine. Based on lessons learned from the oldest metazoan phylum, sponges, it has been recognized that two previously ignored or insufficiently recognized principles play an essential role in tissue regeneration, including biomineral formation/repair and wound healing. Firstly, the dependence on enzymes as a driving force and secondly, the availability of metabolic energy. The discovery of enzymatic synthesis and regenerative activity of amorphous biosilica that builds the mineral skeleton of siliceous sponges formed the basis for the development of successful strategies for the treatment of osteochondral impairments in humans. In addition, the elucidation of the functional significance of a second regeneratively active inorganic material, namely inorganic polyphosphate (polyP) and its amorphous nanoparticles, present from sponges to humans, has pushed forward the development of innovative materials for both soft (skin, cartilage) and hard tissue (bone) repair. This energy-rich molecule exhibits a property not shown by any other biopolymer: the delivery of metabolic energy, even extracellularly, necessary for the ATP-dependent tissue regeneration. This review summarizes the latest developments in nanobiomaterials based on these two evolutionarily old, regeneratively active materials, amorphous silica and amorphous polyP, highlighting their specific, partly unique properties and mode of action, and discussing their possible applications in human therapy. The results of initial proof-of-concept studies on patients demonstrating complete healing of chronic wounds are outlined.

Use of biosilica to improve loading and delivery of bone morphogenic protein 2.

The clinical utility of bone morphogenetic protein 2 (BMP2) is limited because of the poor attraction between BMP2 and carriers, resulting in low loading efficiency and initial burst release. Here, the high binding affinity of BMP2 to the biosilica surface was utilized to overcome this limitation. Atomic force microscopy revealed that BMP2 bound nearly 8- and 2-fold more strongly to biosilica-coated hydroxyapatite than to uncoated and plain silica-coated hydroxyapatite, respectively. To achieve controlled release, collagen was introduced between the silica layers on hydroxyapatite, which was optimized by adjusting the collagen concentration and number of layers. The optimal biosilica/collagen formulation induced sustained BMP2 release without compromising loading efficiency. BMP2 combined with the mentioned formulation led to an increase in osteogenesis, as compared to the combination of BMP2 with either biosilica-coated or non-coated hydroxyapatite in vitro. In rat calvarial defect models, the biosilica/collagen-coated hydroxyapatite with 1 µg BMP2 showed 26 % more bone regeneration than the same dose of BMP2-loaded hydroxyapatite and 10.6 % more than hydroxyapatite with 2.5-fold dose of BMP2. Using BMP2 affinity carriers coated with biosilica/collagen allows for more efficacious in situ loading and delivery of BMP2, making them suitable for the clinical application of growth factors through a soaking method.

The Art of Exploring Diatom Biosilica Biomaterials: From Biofabrication Perspective.

Diatom is a common single-cell microalgae with large species and huge biomass. Diatom biosilica (DB), the shell of diatom, is a natural inorganic material with a micro-nanoporous structure. Its unique hierarchical porous structure gives it great application potential in drug delivery, hemostat materials, and biosensors, etc. However, the structural diversity of DB determines its different biological functions. Screening hundreds of thousands of diatom species for structural features of DB that meet application requirements is like looking for a needle in a seaway. And the chemical modification methods lack effective means to control the micro-nanoporous structure of DB. The formation of DB is a typical biomineralization process, and its structural characteristics are affected by external environmental conditions, genes, and other factors. This allows to manipulate the micro-nanostructure of DB through biological regulation method, thereby transforming the screening mode of the structure function of DB from a needle in a seaway to biofabrication mode. This review focuses on the formation, biological modification, functional activity of DB structure, and its application in biomaterials field, providing regulatory strategies and research idea of DB from the perspective of biofabrication. It will also maximize the possibility of using DB as biological materials.

Using algae in Li-ion batteries: A sustainable pathway toward greener energy storage.

This paper reviews and analyzes the innovations and advances in using algae and their derivatives in different parts of Li-ion batteries. Applications in Li-ion battery anodes, electrolytes, binders, and separators were discussed. Algae provides a sustainable feedstock for different materials that can be used in Li-ion batteries, such as carbonaceous material, biosilica, biopolymers, and other materials that have unique micro- and nano-structures that act as biotemplates for composites structure design. Natural materials and biotemplates provided by algae have various advantages, such as electrochemical and thermal stability, porosity that allows higher storage capacity, nontoxicity, and other properties discussed in the paper. Results reveal that despite algae and its derivatives being a promising renewable feedstock for different applications in Li-ion batteries, more research is yet to be performed to evaluate its feasibility of being used in the industry.